Water-dispersible, cationic polymers, a method of making same and items using same

ABSTRACT

The present invention is directed to triggerable, water-dispersible cationic polymers. The present invention is also directed to a method of making triggerable, water-dispersible cationic polymers and their applicability as binder compositions. The present invention is further directed to fiber-containing fabrics and webs comprising triggerable, water-dispersible binder compositions and their applicability in water-dispersible personal care products, such as wet wipes.

FIELD OF THE INVENTION

[0001] The present invention is directed to ion-sensitive ortriggerable, water-dispersible or water-soluble cationic polymers andpolymer formulations. The present invention is also directed to a methodof making ion-sensitive or triggerable, water-dispersible orwater-soluble cationic polymers and polymer formulations and theirapplicability as binder compositions for disposable items. The presentinvention is further directed to disposable items, such as wet-wipescomprising ion-sensitive or triggerable, water-dispersible bindercompositions including cationic polymer or polymer formulations.

BACKGROUND OF THE INVENTION

[0002] For many years, the problem of disposability has plaguedindustries which provide disposable items, such as, diapers, wet wipes,incontinent garments and feminine care products. While much headway hasbeen made in addressing this problem, one of the weak links has been theinability to create an economical coherent fibrous web, which willreadily dissolve or disintegrate in water, but still have sufficientin-use strength. See, for example, U.K. patent disclosure 2,241,373 andU.S. Pat. No. 4,186,233. Without such a product, the ability of the userto dispose of the product by flushing it down the toilet is greatlyreduced, if not eliminated. Furthermore, the ability of the product todisintegrate in a landfill is quite limited because a large portion ofthe product components, which may well be biodegradable orphotodegradable, are encapsulated in or bound together by plastic whichdegrades over a long period of time, if at all. Accordingly, if theplastic disintegrated in the presence of water, the internal componentscould degrade as a result of the rupture of the plastic encapsulation orbinding.

[0003] Disposable products, such as diapers, feminine care products andadult incontinent care products may be made to be disposed by flushingdown toilets. Usually such products comprise a body side liner whichmust rapidly pass fluids, such as urine or menses, so that the fluid maybe absorbed by an absorbent core of the product. Typically, the bodyside liner may be a coherent fibrous web, which desirably possesses anumber of characteristics, such as softness and flexibility. The fibrousweb of the body side liner material may be typically formed by wet ordry (air) laying a generally random plurality of fibers and joining themtogether to form a coherent web with a binder compositions. Past bindercompositions have preformed this function well. However, fibrous webscomprising these compositions tended to be non-dispersible and presentproblems in typical household sanitation systems.

[0004] Recent binder compositions have been developed which can be moredispersible and are more environmentally responsible than past bindercompositions. One class of binder compositions includes polymericmaterials having inverse solubility in water. These binder compositionsare insoluble in warm water, but are soluble in cold water, such asfound in a toilet. It is well known that a number of polymers exhibitcloud points or inverse solubility properties in aqueous media. Thesepolymers have been cited in several publications for variousapplications, including (1) as evaporation retarders (JP 6207162); (2)as temperature sensitive compositions, which are useful as temperatureindicators due to a sharp color change associated with a correspondingtemperature change (JP 6192527); (3) as heat sensitive materials thatare opaque at a specific temperature and become transparent when cooledto below the specific temperature (JP 51003248 and JP 81035703); (4) aswound dressings with good absorbing characteristics and easy removal (JP6233809); and (5) as materials in flushable personal care products (U.S.Pat. No. 5,509,913, issued to Richard S. Yeo on Apr. 23, 1996 andassigned to Kimberly-Clark Corporation).

[0005] Other recent binders of interest include a class of binders,which are ion-sensitive. Several U.S. and European patents assigned toLion Corporation of Tokyo, Japan, disclose ion-sensitive polymerscomprising acrylic acid and alkyl or aryl acrylates. See U.S. Pat. Nos.5,312,883, 5,317,063 and 5,384,189, the disclosures of which areincorporated herein by reference, as well as, European Pat. No.608460A1. In U.S. Pat. No. 5,312,883, terpolymers are disclosed assuitable binders for flushable nonwoven webs. The disclosed acrylicacid-based terpolymers, which comprise partially neutralized acrylicacid, butyl acrylate and 2-ethylhexyl acrylate, are suitable binders foruse in flushable nonwoven webs in some parts of the world. However,because of the presence of a small amount of sodium acrylate in thepartially neutralized terpolymer, these binders fail to disperse inwater containing more than about 15 ppm Ca²⁺ and/or Mg²⁺. When placed inwater containing more than about 15 ppm Ca²⁺ and/or Mg²⁺ ions, nonwovenwebs using the above-described binders maintain a tensile strengthgreater than 30 g/in, which negatively affects the “dispersibility” ofthe web. The proposed mechanism for the failure is that each calcium ionbinds with two carboxylate groups either intramolecularly orintermolecularly. Intramolecular association causes the polymer chain tocoil up, which eventually leads to polymer precipitation. Intermolecularassociation yields crosslinking. Whether intramolecular orintermolecular associations are taking place, the terpolymer is notsoluble in water containing more than about 15 ppm Ca²⁺ and/or Mg²⁺. Dueto the strong interaction between calcium ions and the carboxylategroups of the terpolymer, dissociation of the complex is highly unlikelybecause this association is irreversible. Therefore, the above-describedpolymer that has been exposed to a high Ca²⁺ and/or Mg²⁺ concentrationsolution will not disperse in water even if the calcium concentrationdecreases. This limits the application of the polymer as a flushablebinder material because most areas across the U.S. have hard water,which contains more than 15 ppm Ca²⁺ and/or Mg²⁺.

[0006] In a co-pending application assigned to Kimberly Clark; i.e.,U.S. patent application Ser. No. 09/223,999, filed Dec. 31, 1998, thedisclosure of which is incorporated herein by reference, there isdisclosed a modification of the acrylic acid terpolymers of theabove-referenced patents to Lion Corporation. Specifically, U.S. patentapplication Ser. No. 09/223,999 discloses a sulfonate anion modifiedacrylic acid terpolymers which has improved dispersibility in relativelyhard water; e.g., up to 200 ppm Ca²⁺ and/or Mg²⁺, compared to theunmodified Lion polymers. The wetted sheet is flexible and soft.However, the Lion Corporation ion-sensitive polymers of theabove-referenced patents and the sulfonate anion modified acrylic acidterpolymers of the co-pending application, when used as binders forpersonal care products, such as wet wipes, typically have reducedinitial sheet wettability, increased dry sheet stiffness, increasedsheet stickiness, reduced binder sprayability and relatively highproduct cost.

[0007] Another approach to dispersible personal care products isdisclosed in U.S. Pat. No. 5,281,306 to Kao Corporation of Tokyo, Japan.This patent discloses a water-disintegratable cleansing sheet; i.e., wetwipe, comprising water-dispersible fibers treated with a water-solublebinder having a carboxyl group. The cleansing sheet is treated with acleansing agent containing 5%-95% of a water-compatible organic solvent,a salt and 95%-5% water. A preferred organic solvent is propyleneglycol. The cleansing sheet retains wet strength and does not dispersein the organic solvent-based cleansing agent, but disperses in water.However, because of the high viscosity of carboxymethylcellulose, whichmakes it difficult to apply to fibrous webs, the presence of an organicsolvent, and the sensitivity to hard water, the composition of thispatent has little commercial applicability.

[0008] Although many patents disclose various ion and temperaturesensitive compositions for water-dispersible or flushable materials,there exists a need for dispersible products possessing softness,flexibility, three dimensionality, and resiliency; wicking andstructural integrity in the presence of body fluids (including feces) atbody temperature; and true fiber dispersion after toilet flushing sothat product does not become entangled with tree roots or at bends insewer pipes. Moreover, there is a need in the art for flushable productshaving water-dispersibility in all areas of the world, including softand hard water areas. Furthermore, there is a need for water-dispersiblebinders that do not reduce wettability of product with which they areused and are sprayable for relatively easy and uniform application toand penetration into products. Finally, there is a need forwater-dispersible, flushable wet wipes that are stable during storageand retain a desired level of wet strength during use and are wettedwith a wetting composition that is relatively free, or is substantiallyfree, of organic solvents. Such a product is needed at a reasonable costwithout compromising product safety and environmental concerns,something that past products have failed to do.

SUMMARY OF THE INVENTION

[0009] The present invention is directed to ion-sensitive cationicpolymers and polymer formulations and to triggerable cationic polymersand polymer formulations, which have been developed to address theabove-described problems associated with currently available,ion-sensitive polymers and other polymers described in literature. Theion-sensitive polymer formulations of the present invention have a“trigger property,” such that the polymers are insoluble in a wettingcomposition comprising an insolublizing agent of a particular type andconcentration, such as monovalent salt solutions at concentrations aboveabout 2%, but are soluble when diluted with water including hard waterwith up to 200 ppm (parts per million) calcium and magnesium ions.Unlike some ion-sensitive polymer formulations, which losedispersibility in hard water because of ion cross-linking by calciumions, the ion-sensitive cationic polymer formulations of the presentinvention are insensitive to calcium and/or magnesium ions atconcentrations of a few hundred ppm and are insensitive to pHvariations. The ion specific cationic polymers and polymer formulationsof the present invention have a “trigger property,” such that thepolymers are insoluble in a wetting composition comprising aninsolublizing agent of a particular type and concentration, such as adivalent metal salt capable of forming complex anion in solution atconcentrations above about 0.5%, but are soluble when diluted with waterincluding other ions, such as divalent salt solutions as found in hardwater with up to 200 ppm (parts per million) calcium and magnesium ions.Consequently, flushable products containing the polymer formulations ofthe present invention maintain dispersibility in hard water or softwater.

[0010] The polymer formulations of the present invention are useful asbinders and structural components for air-laid and wet-laid nonwovenfabrics for applications, such as body-side liners, fluid distributionmaterials, fluid in- take materials (surge) or cover stock in variouspersonal care products. The polymer formulations of the presentinvention are particularly useful as a binder material for flushablepersonal care products, particularly wet wipes for personal use, such ascleaning or treating skin, make-up removal, nail polish removal, medicalcare, and also wipes for use in hard surface cleaning, automotive care,including wipes comprising cleaning agents, disinfectants, and the like.The flushable products maintain integrity or wet strength during storageand use, and break apart or disperse after disposal in the toilet whenthe salt or ion concentration falls below a critical level. Suitablesubstrates for treatment include tissue, such as creped or uncrepedtissue, coform products, hydroentangled webs, airlaid mats, fluff pulp,nonwoven webs, and composites thereof. Methods for producing uncrepedtissues and molded three-dimensional tissue webs of use in the presentinvention can be found in commonly owned U.S. patent application, Ser.No. 08/912,906, “Wet Resilient Webs and Disposable Articles MadeTherewith,” by F. -J. Chen et al., filed Aug. 15, 1997; U.S. Pat. No.5,429,686, issued to Chiu et al. on Jul. 4, 1995; U.S. Pat. No.5,399,412, issued to S. J. Sudall and S. A. Engel on Mar. 21, 1995; U.S.Pat. No. 5,672,248, issued to Wendt et al. on Sept. 30, 1997; and U.S.Pat. No. 5,607,551, issued to Farrington et al. on Mar. 4, 1997; all ofwhich are incorporated herein by reference in their entirety. The moldedtissue structures of the above patents can be especially helpful inproviding good cleaning in a wet wipe. Good cleaning can also bepromoted by providing a degree of texture in other substrates as well byembossing, molding, wetting and through-air drying on a textured fabric,and the like. The cationic polymers and polymer formulations of thepresent invention are particularly useful as a binder for fibrousmaterials because the polymers and polymer formulations are substantiveto the fibers.

[0011] Airlaid material can be formed by metering an airflow containingthe fibers and other optional materials, in substantially dry condition,onto a typically horizontally moving wire forming screen. Suitablesystems and apparatus for air-laying mixtures of fibers andthermoplastic material are disclosed in, for example, U.S. Pat. No.4,157,724 (Persson), issued Jun. 12, 1979, and reissued Dec. 25, 1984 asRe. U.S. Pat. No. 31,775; U.S. Pat. No. 4,278,113 (Persson), issued Jul.14, 1981; U.S. Pat. No. 4,264,289 (Day), issued Apr. 28, 1981; U.S. Pat.No. 4,352,649 (Jacobsen et al.), issued Oct. 5, 1982; U.S. Pat. No.4,353,687 (Hosler, et al.), issued Oct. 12, 1982; U.S. Pat. No.4,494,278 (Kroyer, et al.), issued Jan. 22, 1985; U.S. Pat. No.4,627,806 (Johnson), issued Dec. 9, 1986; U.S. Pat. No. 4,650,409(Nistri, et al.), issued Mar. 17, 1987; and U.S. Pat. No. 4,724,980(Farley), issued Feb. 16, 1988; and U.S. Pat. No. 4,640,810 (Laursen etal.), issued Feb. 3, 1987, the disclosures of which are all incorporatedherein by reference.

[0012] The present invention also discloses how to makewater-dispersible nonwovens, including cover stock (liner), intake(surge) materials and wet wipes, which are stable in fluids having afirst ionic composition, such as monovalent ions or divalent metalcomplex anions at a particular concentration substantially greater thanis found in typical hard water or soft water, using the above-describedunique polymer formulations as binder compositions. The resultantnonwovens are flushable and water-dispersible due to the tailored ionsensitivity, which can be triggered regardless of the hardness of waterfound in toilets throughout the United States and the world.

[0013] The present invention further discloses an improved wettingcomposition for wet wipes. Wet wipes employing the polymer formulationsof the present invention are stable during storage and retain a desiredlevel of wet strength during use and are wetted with a wettingcomposition or cleaning agent that can be relatively free, or issubstantially free, of organic solvents.

[0014] These and other objects, features and advantages of the presentinvention will become apparent after a review of the following detaileddescription of the disclosed embodiments and the appended claims.

DETAILED DESCRIPTION OF THE DISCLOSED EMBODIMENTS

[0015] The present invention can be practiced using two differenttriggerable cationic polymers or polymer compositions. One triggerable,cationic polymer composition is an ion-sensitive cationic polymercomposition and the other is an ion-specific cationic polymer andpolymer composition. These two systems will be discussed further below.Each of these cationic polymer compositions may also optionally includea co-binder, which may be used to alter one or more of the physicalproperties of the cationic polymer composition.

[0016] In order to be an effective ion-sensitive or triggerable cationicpolymer or cationic polymer formulation suitable for use in flushable orwater-dispersible personal care products, the formulations shoulddesirably be (1) functional; i.e., maintain wet strength undercontrolled conditions and dissolve or disperse rapidly in soft or hardwater, such as found in toilets and sinks around the world; (2) safe(not toxic); and (3) relatively economical. In addition to the foregoingfactors, the ion-sensitive or triggerable formulations when used as abinder composition for a non-woven substrate, such as a wet wipe,desirably should be (4) processable on a commercial basis; i.e., may beapplied relatively quickly on a large scale basis, such as by spraying(which thereby requires that the binder composition have a relativelylow viscosity at high shear); and (5) provide acceptable levels of sheetor substrate wettability. The wetting composition with which the wetwipes of the present invention are treated can provide some of theforegoing advantages, and, in addition, can provide one or more of (6)improved skin care, such as reduced skin irritation or other benefits,(7) improved tactile properties, and (8) promote good cleaning byproviding a balance in use between friction and lubricity on the skin(skin glide). The ion-sensitive or triggerable cationic polymers andpolymer formulations of the present invention and articles madetherewith, especially wet wipes comprising particular wettingcompositions set forth below, can meet many or all of the abovecriteria. Of course, it is not necessary for all of the advantages ofthe preferred embodiments of the present invention to be met to fallwithin the scope of the present invention.

[0017] Ion-sensitive Cationic Polymer Compositions

[0018] The ion-sensitive cationic polymers of the present invention maybe formed from two, three or four different monomers. The copolymers ofthe present invention are the polymerization product of a cationicmonomer and at least one hydrophobic monomer. The terpolymers ortetrapolymers of the present invention are the polymerization productsof a cationic monomer, at least one hydrophobic monomer and optionallyat least one hydrophilic monomer or water-soluble nonionic monomer.

[0019] The preferred cationic polymer in the ion-sensitive cationicpolymers of the present invention is [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride.

[0020] Suitable hydrophobic monomers for use in the ion-sensitivecationic polymers of the present invention include, but are not limitedto, alkyl acrylates, such as, butyl acrylate, 2-ethylhexyl acrylate,ethyl acrylate, lauryl acrylate, and hexadecyl acrylate. Methacrylateanalogs of alkyl acrylates are also suitable.

[0021] Suitable hydrophilic monomers or water-soluble nonionic monomersfor use in the ion-sensitive cationic polymers of the present inventioninclude, but are not limited to, acrylamide and methacrylamide basedmonomers, such as acrylamide, N,N-dimethyl acrylamide, N-ethylacrylamide, N-isopropyl acrylamide, and hydroxymethyl acrylamide; andacrylate or methacrylate based monomers include, such as, hydroxyalkylacrylates and hydroxyalkyl methacrylates, such as hydroxyethylmethacrylate, hydroxyethyl acrylate; polyalkoxyl acrylates, such aspolyethyleneglycol acrylates and polyalkoxyl methacrylates, such aspolyethyleneglycol methacrylates (“PEG-MA”). Other suitable hydrophilicmonomers or water-soluble nonionic monomers for use in the ion-sensitivecationic polymers of the present invention include, but are not limitedto, N-vinylpyrrolidinone; and N-vinylformamide.

[0022] A preferred quaternary polymer of the present invention is thepolymerization product of the following four monomers: acrylamide, butylacrylate, 2-ethylhexyl acrylate and [2-(methacryloyloxy)ethyl] trimethylammonium chloride. A preferred terpolymer of the present invention isformed from three different monomers: butyl acrylate, 2-ethylhexylacrylate and [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride. Apreferred copolymer of the present invention is the polymerizationproduct of [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride andbutyl acrylate or 2-ethylhexyl acrylate. An especially preferredterpolymer of the present invention is the polymerization product of[2-(methacryloyloxy)ethyl] trimethyl ammonium chloride and butylacrylate and 2-ethylhexyl acrylate. Acrylamide,[2-(methacryloyloxy)ethyl] trimethyl ammonium chloride, butyl acrylateand 2-ethylhexyl acrylate are all commercially available from AldrichChemical, Milwaukee, Wis.

[0023] For the ion-sensitive quaternary polymer made from acrylamide,butyl acrylate, 2-ethylhexyl acrylate and [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride, the mole percent of monomer in thequaternary polymer is as follows: about 35 to less than 80 mole percentacrylamide; greater than 0 to about 45 mole percent butyl acrylate;greater than 0 to about 65 mole percent 2-ethylhexyl acrylate; andgreater than 0 to about 20 mole percent [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride. More specifically, the mole percent ofmonomers in the quaternary polymer is from about 50 to about 67 molepercent acrylamide; from about 15 to about 28 mole percent butylacrylate; from about 7 to about 15 mole percent 2-ethylhexyl acrylate;and from greater than 0 to about 10 mole percent[2-(methacryloyloxy)ethyl] trimethyl ammonium chloride. Mostspecifically, the mole percent of monomers in the quaternary polymer isfrom about 57 to about 66 mole percent acrylamide; from about 15 toabout 28 mole percent butyl acrylate; from about 7 to about 13 molepercent 2-ethylhexyl acrylate; and about 1 to about 6 mole percent[2-(methacryloyloxy)ethyl] trimethyl ammonium chloride.

[0024] For the ion-sensitive co- and terpolymer made from butylacrylate, 2-ethylhexyl acrylate and [2-(methacryloyloxy)ethyl] trimethylammonium chloride, the mole percent of monomer in the terpolymer is asfollows: from 0 to about 90 mole percent butyl acrylate; from 0 to about75 mole percent 2-ethylhexyl acrylate; and from 5 to about 60 molepercent [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride.

[0025] The ion-sensitive terpolymers and quaternary polymers of thepresent invention may have an average molecular weight, which variesdepending on the ultimate use of the polymer. The quaternary polymers ofthe present invention have a weight average molecular weight rangingfrom about 10,000 to about 5,000,000. More specifically, the quaternarypolymers of the present invention have a weight average molecular weightranging from about 25,000 to about 2,000,000, or, more specificallystill, from about 200,000 to about 1,000,000. The terpolymers of thepresent invention have a weight average molecular weight ranging fromabout 10,000 to about 5,000,000. More specifically, the terpolymers ofthe present invention have a weight average molecular weight rangingfrom about 25,000 to about 2,000,000, or, more specifically still, fromabout 200,000 to about 1,000,000.

[0026] The ion-sensitive terpolymers and quaternary polymers of thepresent invention may be prepared according to a variety ofpolymerization methods, desirably a solution polymerization method.Suitable solvents for the polymerization method include, but are notlimited to, lower alcohols such as methanol, ethanol and propanol; amixed solvent of water and one or more lower alcohols mentioned above;and a mixed solvent of water and one or more lower ketones such asacetone or methyl ethyl ketone.

[0027] In the polymerization methods of the present invention, any freeradical polymerization initiator may be used. Selection of a particularinitiator may depend on a number of factors including, but not limitedto, the polymerization temperature, the solvent, and the monomers used.Suitable polymerization initiators for use in the present inventioninclude, but are not limited to, 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile), 2,2′azobis(2,4-dimethylvaleronitrile),2,2′-azobis(2-amidinopropane)dihydrochloride,2,2′-azobis(N,N′-dimethyleneisobutylamidine), potassium persulfate,ammonium persulfate, and aqueous hydrogen peroxide. The amount ofpolymerization initiator may desirably range from about 0.01 to 5 weightpercent based on the total weight of monomer present.

[0028] The polymerization temperature may vary depending on thepolymerization solvent, monomers, and initiator used, but in general,ranges from about 20° C. to about 90° C. Polymerization time generallyranges from about 2 to about 8 hours.

[0029] In a further embodiment of the present invention, theabove-described ion-sensitive cationic polymer formulations are used asbinder materials for flushable and/or non-flushable products. In orderto be effective as a binder material in flushable products throughoutthe United States, the ion-sensitive polymer formulations of the presentinvention remain stable and maintain their integrity while dry or inrelatively high concentrations of monovalent ions, but become soluble inwater containing up to about 200 ppm or more divalent ions, especiallycalcium and magnesium. Desirably, the ion-sensitive cationic polymerformulations of the present invention are insoluble in a salt solutioncontaining at least about 2 weight percent of one or more inorganicand/or organic salts containing monovalent and/or multivalent ions. Moredesirably, the ion-sensitive cationic polymer formulations of thepresent invention are insoluble in a salt solution containing from about2 weight percent to about 5 weight percent of one or more inorganicand/or organic salts containing monovalent and/or multivalent ions. Evenmore desirably, the ion-sensitive polymer formulations of the presentinvention are insoluble in salt solutions containing from about 2 weightpercent to about 4 weight percent of one or more inorganic and/ororganic salts containing monovalent and/or multivalent ions. Suitablemonovalent ions include, but are not limited to, Na⁺ ions, K⁺, ions, Li⁺ions, NH₄ ⁺ ions, low molecular weight quaternary ammonium compounds(e.g., those having fewer than 5 carbons on any side group), and acombination thereof. Suitable multivalent ions include, but are notlimited to, Zn²⁺ and Ca²⁺.

[0030] Based on a recent study conducted by the American ChemicalSociety, water hardness across the United States varies greatly, withCaCO₃ concentration ranging from near zero for soft water to about 500ppm CaCO₃ (about 200 ppm Ca²⁺ ion) for very hard water. To ensurepolymer formulation dispersibility across the country (and throughoutthe whole world), the ion-sensitive cationic polymer formulations of thepresent invention are desirably soluble in water containing up to about50 ppm Ca²⁺ and/or Mg²⁺ ions. More desirably, the ion-sensitive cationicpolymer formulations of the present invention are soluble in watercontaining up to about 100 ppm Ca²⁺ and/or Mg²⁺ ions. Even moredesirably, the ion-sensitive cationic polymer formulations of thepresent invention are soluble in water containing up to about 150 ppmCa²⁺ and/or Mg²⁺ ions. Even more desirably, the ion-sensitive cationicpolymer formulations of the present invention are soluble in watercontaining up to about 200 ppm Ca²⁺ and/or Mg²⁺ ions.

[0031] Ion-Specific Cationic Polymer Compositions

[0032] The above-described ion-sensitive polymer compositions when usedas a binder for woven or nonwoven substrates, such as wet wipes, helpsmaintain strength in the dry state, or in the wet state by iontriggerability. A high concentration of salt insolubilizes the bindersand allows it to function as an adhesive for the web. This effect isreferred to as “salting out.” The above disclosures identify usefulion-sensitive polymer compositions as well as useful polymer/saltcombinations, which allow for high strength in use and under storageconditions, but allow the web to break apart in the toilet when the saltconcentration falls below the critical level. As a part of the presentinvention, it has been discovered that a broader range of polymercomposition may be useful in such triggerable applications, but themechanism by which those compositions are rendered triggerable ismediated by the salt concentration and type. Thus, ion-specific triggersystems have been discovered that depend on the nature of the cationicpolymer, the cationic species of the salt and the anionic species of thesalt. In addition, it has been discovered that strength/dispersibilityare closely mediated by both ion types. These new cationic polymerbinder/salt combinations can be used to provide ion-specific triggersystems that are not only pH independent and relatively insensitive towater hardness, but function at much lower levels of added salt than theprevious systems. As used herein, the ion-sensitive polymers andion-specific polymers of the present invention will both be referred toas triggerable polymers.

[0033] The ion-specific cationic polymers of the present inventioncomprise 1) a cationic monomer, 2) at least one water insoluble,hydrophobic monomer, and optionally, 3) a hydrophilic and/orwater-soluble nonionic monomer. The cationic monomers useful in thepresent invention include quaternary ammonium monomers, including, butnot limited to, cationic monomer is selected from[2-(methacryloyloxy)ethyl] trimethyl ammonium chloride,(3-acrylamidopropyl) trimethylammonium chloride,N,N-diallyldimethylammonium chloride, acryloxyethyltrimethyl ammoniumchloride, acryloxyethyldimethylbenzyl ammonium chloride,methacryloxyethyldimethyl ammonium chloride,methacryloxyethyltrimethylbenzyl ammonium chloride and quaternized vinylpyridine. Other vinyl functional monomers which when copolymerized witha water insoluble hydrophobic monomer form ionomers in the presence ofdivalent metal complex anions are also useful in the present invention.

[0034] The water insoluble hydrophobic monomers useful in the presentinvention include n-butyl acrylate and 2-ethylhexyl acrylate. Othern-alkyl or branched alkyl, acrylamido, acrylic esters and other vinylfunctional monomers which when copolymerized with the cationic monomerform ionomers or ionomer-like structures in the presence of divalentmetal complex anions are also useful in the present invention.

[0035] The hydrophilic and/or water-soluble nonionic monomer useful inthe present invention include (meth)-acrylamide, substituted(meth)acrylamides, such as diacetone acrylamide, hydroxyalkyl(meth)-acrylate, hydroxyalkyl acrylates, such as hydroxyethyl acrylateor hydroxyethyl methacrylate (HEMA); polyethyleneglycol acrylates,polyethyleneglycol methacrylates, and vinyl pyrrolidone. Other vinylfunctional monomers which when copolymerized with the water insolublehydrophobic monomer and the cationic monomer form ionomers in thepresence of divalent metal complex anions are also useful in the presentinvention.

[0036] The key to developing a successful ion-specific cationic polymerbinder is to control the balance of the hydrophilic and hydrophobicmonomers through a careful study of varying polymer compositions. Also,examination and observation of the binder's performance with specificcation and anion types as shown in the examples below has lead to thedevelopment of a proposed mechanism. Without wanting to be limited inany way by the proposed mechanism, applicants believe that theion-specific polymer compositions of the present invention operate asfollows. These results shown below indicate “ion specific” interactionsrather than the “salting-out” effect seen in previous systems. Althoughionic strength may play a role, the data presented here clearlyindicates a new type of trigger mechanism based on hydrophobicassociations and ion-specific interactions. The nature of this mechanismhas been poorly understood until recently. It is believed that certaindivalent metal ions, such as Zn²⁺, Ca²⁺ and Mg²⁺, form complex ions insolution with halogen anions, such as (ZnCl₄)²⁻(F. Albert Cotton andGeoffrey William, Advanced Inorganic Chemistry, John Wiley and Sons.1980). These complex ions have been isolated as the salts of largecations, such as quaternary ammonium ions. In addition, theseinteractions may become stronger in media of low dielectric constants.Ca²⁺ and Mg²⁺, do not typically form complexes in water, but do so inlower ketones and alcohols (i.e., at lower dielectric constant).

[0037] Therefore, it is believed the mechanism relies upon divalentmetal ions that may form complex anions in the presence of thequaternary ammonium groups of the cationic co- and terpolymers. It isbelieved that these complex ions may “bridge” quaternary ammonium groupson the same polymer molecule or on other molecules and lead to apsuedo-crosslinked structure. Additionally, it is believed that thesecomplex ion clusters organize into ionomer or ionomer-like domains,giving an overall morphology that results in good web strength inrelatively low salt concentrations. Since the formation of the complexanions is highly dependant on the metal and counterion concentrations,the web become re-dispersible upon dilution with water that may containother ions, even relatively high concentrations of other ions, such asfound in hard water.

[0038] For the ion-specific copolymer made from a cationic monomer and awater insoluble, hydrophobic monomer, the mole percent of monomer in thecopolymer is as follows: about 10 to less than 50 mole percent cationicmonomer; and greater than 50 to about 90 mole percent water insoluble,hydrophobic monomer. More specifically, the mole percent of monomers inthe copolymer is from about 15 to about 25 mole percent cationicmonomer; and from about 70 to about 85 mole percent water insoluble,hydrophobic monomer. Most specifically, the mole percent of monomers inthe copolymer is from about 20 mole percent cationic monomer; and about80 mole percent water insoluble, hydrophobic monomer.

[0039] For the ion-specific terpolymer made from a cationic polymer, awater insoluble hydrophobic monomer and a water soluble or hydrophilicmonomer, the mole percent of monomer in the terpolymer is as follows:about 5 to less than 50 mole percent cationic monomer; from about 30 toabout 90 mole percent water insoluble hydrophobic monomer; and fromabout 10 to about 60 mole percent water soluble or hydrophilic monomer.

[0040] The ion-specific copolymers and terpolymers of the presentinvention may have an average molecular weight, which varies dependingon the ultimate use of the polymer. The copolymers and terpolymers ofthe present invention have a weight average molecular weight rangingfrom about 10,000 to about 5,000,000. More specifically, the copolymersand terpolymers of the present invention have a weight average molecularweight ranging from about 25,000 to about 2,000,000, or, morespecifically still, from about 200,000 to about 1,000,000.

[0041] The ion-specific copolymers and terpolymers of the presentinvention may be prepared according to the same free radicalpolymerization methods described above for the ion-sensitive cationicpolymer.

[0042] As stated above, the mechanism of the ion-specific cationicpolymer relies upon the interaction of the polymer cation and the amountand specific type of anion in a wetting solution. It has been discoveredas a part of the present invention that the anion must be a divalentmetal ion that forms a complex anion. Furthermore, the counterion of thedivalent metal ion also seems to plays a role in the operability of thepresent invention. The divalent metal ions that are useful in thepresent invention include Zn²⁺, Ca²⁺ and Mg²⁺. The counter ion for thedivalent metal ion that are useful in the present invention includehalogen ion, particularly Cl⁻, Br⁻ and I⁻. Thus, salts that are usefulin the present invention include ZnCl₂, MgCl₂, and CaCl₂. Other divalentmetal salts that form complex anions in the presence of the quaternaryammonium group of the cationic polymer are also useful in the presentinvention.

[0043] Again, without wishing to be bound by a proposed mechanism, itappears that certain divalent ions, such as Zn²⁺, may form complex ionsin solution with halogen anions, such as (ZnCl₄)²⁻(F. Albert Cotton andGeoffrey William, Advanced Inorganic Chemistry, John Wiley and Sons.1980). These complex ions have been isolated as the salts of largecations, such as quaternary ammonium ions. In addition, theseinteractions may become stronger in media of low dielectric constants.Ca²⁺ and Mg²⁺, do not typically form complexes in water, but do so inlower ketones and alcohols (i.e., at lower dielectric constant).

[0044] Therefore, the mechanism is believed to involve divalent metalions that form complex anions in the presence of the quaternary ammoniumgroups of the co- and terpolymers. It is believed that these complexions “bridge” quaternary ammonium groups on the same polymer molecule oron other molecules and lead to a psuedo-crosslinked structure.Additionally, it is believed that these complex ion clusters organizedinto ionomers, giving an overall morphology that results in good webstrength in solutions containing specific amounts and types of salts.Since the formation of the complex anions is highly dependant on themetal and counterion concentrations, the web become re-dispersible upondilution with water that does not contain the critical amount of thesecomplex anions, but may contain other mono or divalent ions, such asfound in hard or soft water.

[0045] In a further embodiment of the present invention, theabove-described ion-specific cationic polymer formulations are used asbinder materials for flushable and/or non-flushable products. In orderto be effective as a binder material in flushable products throughoutthe United States, the ion-specific cationic polymer formulations of thepresent invention remain stable and maintain their integrity while dryor in relatively high concentrations of ions, but become soluble inwater containing up to about 200 ppm or more divalent ions, especiallycalcium, magnesium and sulfonate ions. Desirably, the ion-specificcationic polymer formulations of the present invention are insoluble ina solution containing at least about 0.5 weight percent of one or moredivalent metal salts capable of forming complex anions. More desirably,the ion-specific cationic polymer formulations of the present inventionare insoluble in a solution containing from about 1 weight percent toabout 5 weight percent of one or more divalent metal salts capable offorming complex anions. Even more desirably, the ion-specific cationicpolymer formulations of the present invention are insoluble in solutionscontaining from about 2 weight percent to about 4 weight percent of oneor more divalent metal salts capable of forming complex anions.

[0046] To ensure polymer formulation dispersibility across the country(and throughout the whole world), the ion-specific cationic polymerformulations of the present invention are desirably soluble in watercontaining up to about 50 ppm Ca²⁺ and/or Mg²⁺ ions. More desirably, theion-specific cationic polymer formulations of the present invention aresoluble in water containing up to about 100 ppm Ca²⁺ and/or Mg²⁺ ions.Even more desirably, the ion-specific cationic polymer formulations ofthe present invention are soluble in water containing up to about 150ppm Ca²⁺ and/or Mg²⁺ ions. Even more desirably, the ion-specificcationic polymer formulations of the present invention are soluble inwater containing up to about 200 ppm Ca²⁺ and/or Mg²⁺ ions.

[0047] Co-binder Polymers

[0048] As stated above, the cationic polymer formulations of the presentinvention are formed from a single triggerable polymer or a combinationof two or more different polymers, wherein at least one polymer is atriggerable polymer. The second polymer may be a co-binder polymer. Aco-binder polymer is of a type and in an amount such that when combinedwith the triggerable polymer, the co-binder polymer desirably is largelydispersed in the triggerable polymer; i.e., the triggerable polymer isdesirably the continuous phase and the co-binder polymer is desirablythe discontinuous phase. Desirably, the co-binder polymer can also meetseveral additional criteria. For example, the co-binder polymer can havea glass transition temperature; i.e., T_(g), that is lower than theglass transition temperature of the triggerable polymer. Furthermore oralternatively, the co-binder polymer can be insoluble in water, or canreduce the shear viscosity of the triggerable polymer. The co-binder canbe present at a level relative to the solids mass of the triggerablepolymer of about 45% or less, specifically about 30% or less, morespecifically about 20% or less, more specifically still about 15% orless, and most specifically about 10% or less, with exemplary ranges offrom about 1% to about 45% or from about 25% to about 35%, as well asfrom about 1% to about 20% or from about 5% to about 25%. The amount ofco binder present should be low enough, for co-binders with thepotential to form water insoluble bonds or films, that the co-binderremains a discontinuous phase unable to create enough crosslinked, orinsoluble bonds, to jeopardize the dispersibility of the treatedsubstrate. In one embodiment, the polymer formulation of the presentinvention can comprise about 75 weight percent triggerable polymer andabout 25 weight percent co-binder.

[0049] Desirably, but not necessarily, the co-binder polymer whencombined with the triggerable polymer will reduce the shear viscosity ofthe triggerable polymer to such an extent that the combination of thetriggerable polymer and the co-binder polymer is sprayable. By sprayableis meant that the polymer can be applied to a nonwoven fibrous substrateby spraying and the distribution of the polymer across the substrate andthe penetration of the polymer into the substrate are such that thepolymer formulation is uniformly applied to the substrate.

[0050] The co-binder polymer can be in the form of an emulsion latex.The surfactant system used in such a latex emulsion should be such thatit does not substantially interfere with the dispersibility of thetriggerable polymer.

[0051] In some embodiments, the combination of the triggerable polymerand the co-binder polymer reduces the stiffness of the article to whichit is applied compared to the article with just the triggerable polymer.It has been found that when the triggerable polymer is applied to anonwoven substrate, such as an air laid layer of wood pulp, for thepurpose of forming a wet wipe, the nonwoven sheet can have anundesirable amount of stiffness that is detrimental to the dry productfeel or to the handling of the dry web during processing, when thebrittleness of the dry substrate can harm runnability. By combining thetriggerable polymer and the co-binder polymer, the stiffness of sucharticles can be reduced.

[0052] The co-binder polymer of the present invention can have anaverage molecular weight, which varies depending on the ultimate use ofthe polymer. Desirably, the co-binder polymer has a weight averagemolecular weight ranging from about 500,000 to about 200,000,000. Moredesirably, the co-binder polymer has a weight average molecular weightranging from about 500,000 to about 100,000,000.

[0053] Co-binder polymers that can meet many or all of the foregoingcriteria include, but are not limited to, poly(ethylene-vinyl acetate),poly(styrene-butadiene), poly(styrene-acrylic), a vinyl acrylicterpolymer, neoprene, a polyester latex, an acrylic emulsion latex, polyvinyl chloride, ethylene-vinyl chloride copolymer, a carboxylated vinylacetate latex, and the like, all of which can be non-crosslinking (e.g.,devoid of N-methylol acrylamide or other crosslinkers), crosslinking, orpotentially crosslinking (i.e., prepared with a crosslinker present) butnot substantially crosslinked in the final product.

[0054] A particularly preferred non-crosslinking poly(ethylene-vinylacetate) is Dur-O-Set® RB available from National Starch and ChemicalCo., Bridgewater, N.J. A particularly preferred non-crosslinkingpoly(styrene-butadiene) is Rovene® 4817 available from Mallard CreekPolymers, Charlotte, N.C. A particularly preferred non-crosslinkingpoly(styrene-acrylic) is Rhoplex® NM 1715K available from Rohm and Haas,Philadelphia, Pa.

[0055] When a latex co-binder, or any potentially crosslinkableco-binder is used, the latex should be prevented from formingsubstantial water-insoluble bonds that bind the fibrous substratetogether and interfere with the dispersibility of the article. Thus, thelatex can be free of crosslinking agents, such as NMA, or free ofcatalyst for the crosslinker, or both. Alternatively, an inhibitor canbe added that interferes with the crosslinker or with the catalyst suchthat crosslinking is impaired even when the article is heated to normalcrosslinking temperatures. Such inhibitors can include free radicalscavengers, methyl hydroquinone, t-butylcatechol, pH control agents suchas potassium hydroxide, and the like. For some latex crosslinkers, suchas N-methylol-acrylamide (NMA), for example, elevated pH such as a pH of8 or higher can interfere with crosslinking at normal crosslinkingtemperatures (e.g., about 130° C. or higher). Also alternatively, anarticle comprising a latex co-binder can be maintained at temperaturesbelow the temperature range at which crosslinking takes place, such thatthe presence of a crosslinker does not lead to crosslinking, or suchthat the degree of crosslinking remains sufficiently low that thedispersibility of the article is not jeopardized. Also alternatively,the amount of crosslinkable latex can be kept below a threshold levelsuch that even with crosslinking, the article remains dispersible. Forexample, a small quantity of crosslinkable latex dispersed as discreteparticles in an ion-sensitive binder can permit dispersibility even whenfully crosslinked. For the later embodiment, the amount of latex can bebelow about 20 weight percent, and, more specifically, below about 15weight percent relative to the ion-sensitive binder.

[0056] Latex compounds, whether crosslinkable or not, need not be theco-binder. SEM micrography of successful ion-sensitive binder films withuseful non-crosslinking latex emulsions dispersed therein has shown thatthe latex co-binder particles can remain as discrete entities in theion-sensitive binder, possibly serving in part as filler material. It isbelieved that other materials could serve a similar role, including adispersed mineral or particulate filler in the triggerable binder,optionally comprising added surfactants/dispersants. For example, in oneenvisioned embodiment, freeflowing Ganzpearl PS-8F particles fromPresperse, Inc. (Piscataway, N.J.), a styrene/divinylbenzene copolymerwith about 0.4 micron particles, can be dispersed in a triggerablebinder at a level of about 2 to 10 weight percent to modify themechanical, tactile, and optical properties of the triggerable binder.Other filler-like approaches may include microparticles, microspheres,or microbeads of metal, glass, carbon, mineral, quartz, and/or plastic,such as acrylic or phenolic, and hollow particles having inert gaseousatmospheres sealed within their interiors. Examples include EXPANCELphenolic microspheres from Expancel of Sweden, which expandsubstantially when heated, or the acrylic microspheres known as PM 6545available from PQ Corporation of Pennsylvania. Foaming agents, includingCO₂ dissolved in the triggerable binder, could also provide helpfuldiscontinuities as gas bubbles in the matrix of an triggerable binder,allowing the dispersed gas phase in the triggerable binder to serve asthe co-binder. In general, any compatible material that is not misciblewith the binder, especially one with adhesive or binding properties ofits own, can be used as the co-binder, if it is not provided in a statethat imparts substantial covalent bonds joining fibers in a way thatinterferes with the water-dispersibility of the product. However, thosematerials that also provide additional benefits, such as reduced sprayviscosity, can be especially preferred. Adhesive co-binders, such aslatex that do not contain crosslinkers or contain reduced amounts ofcrosslinkers, have been found to be especially helpful in providing goodresults over a wide range of processing conditions, including drying atelevated temperatures.

[0057] As stated above, the T_(g) of the co-binder polymer can be lowerthan the T_(g) of the triggerable polymer, which is believed to improvethe flexibility of the treated substrate, especially in the dry state.In Table 1 shown below is a comparison of the glass transitiontemperature of some of the preferred polymers useful in the presentinvention. TABLE 1 Glass Transition Temperatures For Select PolymersPolymer Glass Transition Temperature - Tg Cationic Sample #1 fromExample 2  15° C. below Cationic Sample #6 from Example 2  24° C. belowRhoplex NW 1715 K (dry)  −6° C. Rovene 4817 (dry)  −4° C. Elite 33 (dry)−10° C. Elite 22 (dry) −15° C.

[0058] In an alternate embodiment, the triggerable polymer formulationsof the present invention comprises about 55 to about 95 weight percenttriggerable polymer and about 5 to about 45 weight percentpoly(ethylene-vinyl acetate). More desirably, the triggerable polymerformulations of the present invention comprises about 75 weight percenttriggerable polymer and about 25 weight percent poly(ethylene-vinylacetate).

[0059] As stated above, useful co-binder polymers can include a varietyof commercial latex emulsions, including those selected from the Rovene®series (styrene butadiene lattices available from Mallard Creek Polymersof Charlotte, N.C.), the Rhoplex® latices of Rohm and Haas Company, andthe Elite® latices of National Starch. Polymer emulsions or dispersionsgenerally comprise small polymer particles, such as crosslinkableethylene vinyl acetate copolymers, typically in spherical form,dispersed in water and stabilized with surface active ingredients, suchas low molecular weight emulsifiers or high molecular weight protectivecolloids. Care must be taken in selecting the proper emulsion system sothat the emulsion will not interact with the cationic binder tointerfere with the trigger property.

[0060] These liquid binders can be applied to airlaid webs or othersubstrates by methods known in the art of binder treatment for nonwovenwebs, including spray or foam application, flooded nip impregnation,curtain coating, etc., followed by drying. In general, a wide variety oflatex compounds and other resins or emulsions can be considered,including vinyl acetate copolymer latices, such as 76 RES 7800 fromUnion Oil Chemicals Divisions and Duroset RB®, Resyn® 25-1103, Resyn®25-1109, Resyn® 25-1119, and Resyn® 25-1189 from National Starch andChemical Corporation, ethylene-vinyl acetate copolymer emulsions, suchas Airflex® ethylene-vinylacetatek from Air Products and Chemicals Inc.,acrylic-vinyl acetate copolymer emulsions, such as Rhoplex® AR-74 fromRohm and Haas Company, Synthemul® 97-726 from Reichhold Chemicals Inc.,Resyn® 25-1140, 25-1141, 25-1142, and Resyn-6820 from National Starchand Chemical Corporation, vinyl acrylic terpolymer latices, such as 76RES 3103 from Union Oil Chemical Division, and Resyn® 251110 fromNational Starch and Chemical Corporation, acrylic emulsion latices, suchas Rhoplex® B-15J, Rhoplex® P-376, Rhoplex® TR-407, Rhoplex® E-940,Rhoplex® TR934, Rhoplex® TR-520, Rhoplex® HA-24, and Rhoplex® NW1825from Rohm and Haas Company, and Hycar® 2600 X 322, Hycar® 2671, Hycar®2679, Hycar® 26120, and Hycar® 2600 X347 from B. F. Goodrich ChemicalGroup, styrene-butadiene latices, such as 76 RES 4100 and 76 RES 8100available from Union Oil Chemicals Division, Tylac® resin emulsion68-412, Tylac® resin emulsion 68-067, 68-319, 68-413, 68-500, 68-501,available from Reichhold Chemical Inc., and DL6672A, DL6663A, DL6638A,DL6626A, DL6620A, DL615A, DL617A, DL620A, DL640A, DL650A available fromDow Chemical Company; and rubber latices, such as neoprene availablefrom Serva Biochemicals; polyester latices, such as Eastman AQ 29Davailable from Eastman Chemical Company; vinyl chloride latices, such asGeon® 352 from B. F. Goodrich Chemical Group; ethylene-vinyl chloridecopolymer emulsions, such as Airflex® ethylene-vinyl chloride from AirProducts and Chemicals; polyvinyl acetate homopolymer emulsions, such asVinac® from Air Products and Chemicals; carboxylated vinyl acetateemulsion resins, such as Synthemul® synthetic resin emulsions 40-502,40-503, and 97-664 from Reichhold Chemicals Inc. and Polyco® 2149, 2150,and 2171 from Rohm and Haas Company. Silicone emulsions and binders canalso be considered.

[0061] The co-binder polymer can comprise surface active compounds thatimprove the wettability of the substrate after application of the bindermixture. Wettability of a dry substrate that has been treated with atriggerable polymer formulation can be a problem in some embodiments,because the hydrophobic portions of the triggerable polymer formulationcan become selectively oriented toward the air phase during drying,creating a hydrophobic surface that can be difficult to wet when thewetting composition is later applied unless surfactants are added to thewetting composition. Surfactants, or other surface active ingredients,in co binder polymers can improve the wettability of the dried substratethat has been treated with a triggerable polymer formulation.Surfactants in the co-binder polymer should not significantly interferewith the triggerable polymer formulation. Thus, the binder shouldmaintain good integrity and tactile properties in the pre-moistenedwipes with the surfactant present.

[0062] In one embodiment, an effective co-binder polymer replaces aportion of the triggerable polymer formulation and permits a givenstrength level to be achieved in a pre-moistened wipe with at least oneof lower stiffness, better tactile properties (e.g., lubricity orsmoothness), or reduced cost, relative to an otherwise identicalpre-moistened wipe lacking the co-binder polymer and comprising thetriggerable polymer formulation at a level sufficient to achieve thegiven tensile strength.

[0063] Other Co-binder Polymers

[0064] The Dry Emulsion Powder (DEP) binders of Wacker Polymer Systems(Burghausen, Germany) such as the VINNEK® system of binders, can beapplied in some embodiments of the present invention. These areredispersible, free flowing binder powders formed from liquid emulsions.Small polymer particles from a dispersion are provided in a protectivematrix of water soluble protective colloids in the form of a powderparticle. The surface of the powder particle is protected against cakingby platelets of mineral crystals. As a result, polymer particles thatonce were in a liquid dispersion are now available in a free flowing,dry powder form that can be redispersed in water or turned into swollen,tacky particles by the addition of moisture. These particles can beapplied in highloft nonwovens by depositing them with the fibers duringthe airlaid process, and then later adding 10% to 30% moisture to causethe particles to swell and adhere to the fibers. This can be called the“chewing gum effect,” meaning that the dry, non-tacky fibers in the webbecome sticky like chewing gum once moistened. Good adhesion to polarsurfaces and other surfaces is obtained. These binders are available asfree flowing particles formed from latex emulsions that have been driedand treated with agents to prevent cohesion in the dry state. They canbe entrained in air and deposited with fibers during the airlaidprocess, or can be applied to a substrate by electrostatic means, bydirect contact, by gravity feed devices, and other means. They can beapplied apart from the binder, either before or after the binder hasbeen dried. Contact with moisture, either as liquid or steam, rehydratesthe latex particles and causes them to swell and to adhere to thefibers. Drying and heating to elevated temperatures (e.g., above 160°C.) causes the binder particles to become crosslinked and waterresistant, but drying at lower temperatures (e.g., at 110° C. or less)can result in film formation and a degree of fiber binding withoutseriously impairing the water dispersibility of the pre-moistened wipes.Thus, it is believed that the commercial product can be used withoutreducing the amount of crosslinker by controlling the curing of theco-binder polymer, such as limiting the time and temperature of dryingto provide a degree of bonding without significant crosslinking.

[0065] As pointed out by Dr. Klaus Kohlhammer in “New Airlaid Binders,”Nonwovens Report International, September 1999, issue 342, pp. 20 22,28-31, dry emulsion binder powders have the advantage that they caneasily be incorporated into a nonwoven or airlaid web during formationof the web, as opposed to applying the material to an existingsubstrate, permitting increased control over placement of the co-binderpolymer. Thus, a nonwoven or airlaid web can be prepared already havingdry emulsion binders therein, followed by moistening when theion-sensitive polymer formulation solution is applied, whereupon the dryemulsion powder becomes tacky and contributes to binding of thesubstrate. Alternatively, the dry emulsion powder can be entrapped inthe substrate by a filtration mechanism after the substrate has beentreated with triggerable binder and dried, whereupon the dry emulsionpowder is rendered tacky upon application of the wetting composition.

[0066] In another embodiment, the dry emulsion powder is dispersed intothe triggerable polymer formulation solution either by application ofthe powder as the triggerable polymer formulation solution is beingsprayed onto the web or by adding and dispersing the dry emulsion powderparticles into the triggerable polymer formulation solution, after whichthe mixture is applied to a web by spraying, by foam applicationmethods, or by other techniques known in the art.

[0067] Binder Formulations and Fabrics Containing the Same

[0068] The triggerable polymer formulations of the present invention maybe used as binders. The triggerable binder formulations of the presentinvention may be applied to any fibrous substrate. The binders areparticularly suitable for use in water-dispersible products. Suitablefibrous substrates include, but are not limited to, nonwoven and wovenfabrics. In many embodiments, particularly personal care products,preferred substrates are nonwoven fabrics. As used herein, the term“nonwoven fabric” refers to a fabric that has a structure of individualfibers or filaments randomly arranged in a mat-like fashion (includingpapers). Nonwoven fabrics can be made from a variety of processesincluding, but not limited to, air-laid processes, wet-laid processes,hydroentangling processes, staple fiber carding and bonding, andsolution spinning.

[0069] The triggerable binder composition may be applied to the fibroussubstrate by any known process of application. Suitable processes forapplying the binder material include, but are not limited to, printing,spraying, electrostatic spraying, coating, flooded nips, metered pressrolls, impregnating or by any other technique,. The amount of bindercomposition may be metered and distributed uniformly within the fibroussubstrate or may be non-uniformly distributed within the fibroussubstrate. The binder composition may be distributed throughout theentire fibrous substrate or it may be distributed within a multiplicityof small closely spaced areas. In most embodiments, uniform distributionof binder composition is desired.

[0070] For ease of application to the fibrous substrate, the triggerablebinder may be dissolved in water, or in a non-aqueous solvent, such asmethanol, ethanol, acetone, or the like, with water being the preferredsolvent. The amount of binder dissolved in the solvent may varydepending on the polymer used and the fabric application. Desirably, thebinder solution contains up to about 50 percent by weight of bindercomposition solids. More desirably, the binder solution contains fromabout 10 to 30 percent by weight of binder composition solids,especially about 15-25 percent by weight binder composition solids.Plasticizers, perfumes, coloring agents, antifoams, bactericides,preservative, surface active agents, thickening agents, fillers,opacifiers, tackifiers, detackifiers, and similar additives can beincorporated into the solution of binder components, if so desired.

[0071] Once the triggerable binder composition is applied to thesubstrate, the substrate is dried by any conventional means. Once dry,the coherent fibrous substrate exhibits improved tensile strength whencompared to the tensile strength of the untreated wet-laid or dry-laidsubstrates, and yet has the ability to rapidly “fall apart”, ordisintegrate when placed in soft or hard water having a relatively highmultivalent ionic concentration and agitated. For example, the drytensile strength of the fibrous substrate may be increased by at least25 percent as compared to the dry tensile strength of the untreatedsubstrate not containing the binder. More particularly, the dry tensilestrength of the fibrous substrate may be increase by at least 100percent as compared to the dry tensile strength of the untreatedsubstrate not containing the binder. Even more particularly, the drytensile strength of the fibrous substrate may be increased by at least500 percent as compared to the dry tensile strength of the untreatedsubstrate not containing the binder.

[0072] A desirable feature of the present invention is that theimprovement in tensile strength is effected where the amount of bindercomposition present, “add-on”, in the resultant fibrous substraterepresents only a small portion by weight of the entire substrate. Theamount of “add-on” can vary for a particular application; however, theoptimum amount of “add-on” results in a fibrous substrate which hasintegrity while in use and also quickly disperses when agitated inwater. For example, the binder components typically are from about 5 toabout 65 percent, by weight, of the total weight of the substrate. Moreparticularly, the binder components may be from about 10 to about 35percent, by weight, of the total weight of the substrate. Even moreparticularly, the binder components may be from about 17 to about 22percent by weight of the total weight of the substrate.

[0073] The nonwoven fabrics of the present invention have good in-usetensile strength, as well as, ion triggerability. Desirably, thenonwoven fabrics of the present invention are abrasion resistant andretain significant tensile strength in aqueous solutions containing thespecific amount and type of ions disclosed above. Because of this latterproperty, nonwoven fabrics of the present invention are well suited fordisposable products, such as sanitary napkins, diapers, adultincontinence products, and dry and premoistened wipes (wet wipes), whichcan be thrown in a flush toilet after use in any part of the world.

[0074] The fibers forming the fabrics above can be made from a varietyof materials including natural fibers, synthetic fibers, andcombinations thereof. The choice of fibers depends upon, for example,the intended end use of the finished fabric and fiber cost. Forinstance, suitable fibrous substrates may include, but are not limitedto, natural fibers such as cotton, linen, jute, hemp, wool, wood pulp,etc. Similarly, regenerated cellulosic fibers, such as viscose rayon andcuprammonium rayon, modified cellulosic fibers, such as celluloseacetate, or synthetic fibers, such as those derived from polypropylenes,polyethylenes, polyolefins, polyesters, polyamides, polyacrylics, etc.,alone or in combination with one another, may likewise be used. Blendsof one or more of the above fibers may also be used, if so desired.Among wood pulp fibers, any known papermaking fibers may be used,including softwood and hardwood fibers. Fibers, for example, may bechemically pulped or mechanically pulped, bleached or unbleached, virginor recycled, high yield or low yield, and the like. Mercerized,chemically stiffened or crosslinked fibers may also be used.

[0075] Synthetic cellulose fiber types include rayon in all itsvarieties and other fibers derived from viscose or chemically modifiedcellulose, including regenerated cellulose and solvent-spun cellulose,such as Lyocell. Chemically treated natural cellulosic fibers can beused, such as mercerized pulps, chemically stiffened or crosslinkedfibers, or sulfonated fibers. Recycled fibers, as well as virgin fibers,can be used. Cellulose produced by microbes and other cellulosicderivatives can be used. As used herein, the term “cellulosic” is meantto include any material having cellulose as a major constituent, and,specifically, comprising at least 50 percent by weight cellulose or acellulose derivative. Thus, the term includes cotton, typical woodpulps, non-woody cellulosic fibers, cellulose acetate, cellulosetriacetate, rayon, thermomechanical wood pulp, chemical wood pulp,debonded chemical wood pulp, milkweed, or bacterial cellulose.

[0076] The triggerable binder of the present invention may also beapplied to other fibers or particles. Other fibers that may be treatedwith the triggerable binder of the present invention such as fibers madefrom carboxymethyl cellulose, chitin, and chitiosan. The triggerablebinder of the present invention may also be applied to particles, suchas sodium polyacrylate super absorbent particles. Super absorbentparticles are frequently incorporated on or into fibrous substrates usedfor personal care items, especially nonwoven fabrics.

[0077] The fiber length is important in producing the fabrics of thepresent invention. In some embodiments, such as flushable products,fiber length is of more importance. The minimum length of the fibersdepends on the method selected for forming the fibrous substrate. Forexample, where the fibrous substrate is formed by carding, the length ofthe fiber should usually be at least about 42 mm in order to insureuniformity.

[0078] Where the fibrous substrate is formed by air-laid or wet-laidprocesses, the fiber length may desirably be about 0.2 to 6 mm. Althoughfibers having a length of greater than 50 mm are within the scope of thepresent invention, it has been determined that when a substantialquantity of fibers having a length greater than about 15 mm is placed ina flushable fabric, though the fibers will disperse and separate inwater, their length tends to form “ropes” of fibers, which areundesirable when flushing in home toilets. Therefore, for theseproducts, it is desired that the fiber length be about 15 mm or less sothat the fibers will not have a tendency to “rope” when they are flushedthrough a toilet. Although fibers of various lengths are applicable inthe present invention, desirably fibers are of a length less than about15 mm so that the fibers disperse easily from one another when incontact with water. The fibers, particularly synthetic fibers, can alsobe crimped.

[0079] The fabrics of the present invention may be formed from a singlelayer or multiple layers. In the case of multiple layers, the layers aregenerally positioned in a juxtaposed or surface-to-surface relationshipand all or a portion of the layers may be bound to adjacent layers.Nonwoven webs of the present invention may also be formed from aplurality of separate nonwoven webs wherein the separate nonwoven websmay be formed from single or multiple layers. In those instances wherethe nonwoven web includes multiple layers, the entire thickness of thenonwoven web may be subjected to a binder application or each individuallayer may be separately subjected to a binder application and thencombined with other layers in a juxtaposed relationship to form thefinished nonwoven web.

[0080] In one embodiment, the fabric substrates of the present inventionmay be incorporated into cleansing and body fluid absorbent products,such as sanitary napkins, diapers, adult incontinence products, surgicaldressings, tissues, wet wipes, and the like. These products may includean absorbent core, comprising one or more layers of an absorbent fibrousmaterial. The core may also comprise one or more layers of afluid-pervious element, such as fibrous tissue, gauze, plastic netting,etc. These are generally useful as wrapping materials to hold thecomponents of the core together. Additionally, the core may comprise afluid-impervious element or barrier means to preclude the passage offluid through the core and on the outer surfaces of the product.Desirably, the barrier means also is water-dispersible. A film of apolymer having substantially the same composition as the aforesaidwater-dispersible binder is particularly well-suited for this purpose.In accordance with the present invention, the polymer compositions areuseful for forming each of the above-mentioned product componentsincluding the layers of absorbent core, the fluid-pervious element, thewrapping materials, and the fluid-impervious element or barrier means.

[0081] The triggerable binder formulations of the present invention areparticularly useful for binding fibers of air-laid nonwoven fabrics.These air-laid materials are useful for body-side liners, fluiddistribution materials, fluid in-take materials, such as a surgematerial, absorbent wrap sheet and cover stock for variouswater-dispersible personal care products. Air-laid materials areparticularly useful for use as a pre-moistened wipe (wet wipe). Thebasis weights for air-laid non-woven fabrics may range from about 20 toabout 200 grams per square meter (“gsm”) with staple fibers having adenier of about 0.5-10 and a length of about 6-15 millimeters. Surge, orin-take, materials need better resiliency and higher loft so staplefibers having about 6 denier or greater are used to make these products.A desirable final density for the surge, or in-take, materials isbetween about 0.025 grams per cubic centimeter (“g/cc”) to about 0.10g/cc. Fluid distribution materials may have a higher density, in thedesired range of about 0.10 to about 0.20 g/cc using fibers of lowerdenier, most desirable fibers have a denier of less than about 1.5.Wipes generally can have a fiber density of about 0.025 g/cc to about0.2 g/cc and a basis weight of about 20 gsm to about 150 gsm;specifically from about 30 to about 90 gsm, and most specifically fromabout 60 gsm to about 65 gsm.

[0082] The nonwoven fabrics of the present invention may also beincorporated into such body fluid absorbing products as sanitarynapkins, diapers, surgical dressings, tissues and the like. In oneembodiment, the triggerable binder is such that it will not dissolvewhen contacted by body fluids since the concentration of monovalent ionsin the body fluids is above the level needed for dissolution; i.e.,greater than 2% by weight. The nonwoven fabric retains its structure,softness and exhibits a toughness satisfactory for practical use.However, when brought into contact with water having a concentration ofmultivalent ions, such as Ca²⁺ and Mg²⁺ ions, of up to about 200 ppm ormore, the binder disperses. The nonwoven fabric structure is then easilybroken and dispersed in the water.

[0083] In one embodiment of the present invention, the in-use tensilestrength of a nonwoven fabric is enhanced by forming the nonwoven fabricwith a binder material comprising the triggerable polymer formulation ofthe present invention and subsequently applying either one or moremonovalent and/or multivalent salts to the nonwoven fabric or salts ofdivalent metal ions that form complex anions. The salt may be applied tothe nonwoven fabric by any method known to those of ordinary skill inthe art including, but not limited to, applying a solid powder onto thefabric and spraying a salt solution onto the fabric. The amount of saltmay vary depending on a particular application. However, the amount ofsalt applied to the fabric is typically from about 0.5 weight percent toabout 10 weight percent salt solids based on the total weight of thefabric. The salt-containing fabrics of the present invention may be usedin a variety of fabric applications including, but not limited to,feminine pads, surgical dressings, and diapers.

[0084] Those skilled in the art will readily understand that the binderformulations and fibrous substrates of the present invention may beadvantageously employed in the preparation of a wide variety ofproducts, including but not limited to, absorbent personal care productsdesigned to be contacted with body fluids. Such products may onlycomprise a single layer of the fibrous substrate, or may comprise acombination of elements, as described above. Although the binderformulations and fibrous substrates of the present invention areparticularly suited for personal care products, the binder formulationsand fibrous substrates may be advantageously employed in a wide varietyof consumer products.

[0085] Unlike other binder systems known in the art, the triggerablepolymer formulations of the present invention can be activated asbinders without the need for elevated temperature. While drying or waterremoval is useful in achieving a good distribution of the binder in afibrous web, elevated temperature, per se, is not essential because thebinder does not require crosslinking or other chemical reactions withhigh activation energy to serve as a binder. Rather, the interactionwith a soluble insolubilizing compound, typically a salt, is sufficientto cause the binder to become insoluble; i.e., “salted out” or activatedby interaction between the cation of the polymer and the divalent metalcomplex anion from the salt. Thus, a drying step can be avoided, ifdesired, or replaced with low-temperature water removal operations suchas room-temperature drying or freeze drying. Elevated temperature isgenerally helpful for drying, but the drying can be done at temperaturesbelow what is normally needed to drive crosslinking reactions. Thus, thepeak temperature to which the substrate is exposed or to which thesubstrate is brought can be below any of the following: 180° C., 160°C., 140° C., 120° C., 110° C., 105° C., 100° C., 90° C., 75° C., and 60°C., with an exemplary range for peak web temperature of from about 50°C. to about 110° C., or from about 70° C. to about 140° C. Of course,higher temperatures can be used, but are not necessary in mostembodiments. While polymer systems, such as commercial latex emulsions,may also comprise crosslinkers suited for reaction at temperatures of160° C. or higher, maintaining a lower peak temperature can bebeneficial in preventing development of excessive strength in thepolymer that might otherwise hinder the water dispersibility of thepre-moistened wipe.

[0086] Wet Wipe Wetting Composition and Wet Wipes Containing the Same

[0087] One particularly interesting embodiment of the present inventionis the production of pre-moistened wipes, or wet wipes, from theabove-described triggerable binder compositions and fibrous materials.For wipes, the fibrous material may be in the form of a woven ornonwoven fabric; however, nonwoven fabrics are more desirable. Thenonwoven fabric is desirably formed from relatively short fibers, suchas wood pulp fibers. The minimum length of the fibers depends on themethod selected for forming the nonwoven fabric. Where the nonwovenfabric is formed by a wet or dry method, the fiber length is desirablyfrom about 0.1 millimeters to 15 millimeters. Desirably, the nonwovenfabric of the present invention has a relatively low wet cohesivestrength when it is not bonded together by an adhesive or bindermaterial. When such nonwoven fabrics are bonded together by a bindercomposition, which loses its bonding strength in tap water and in sewerwater, the fabric will break up readily by the agitation provided byflushing and moving through the sewer pipes.

[0088] The finished wipes may be individually packaged, desirably in afolded condition, in a moisture proof envelope or packaged in containersholding any desired number of sheets in a water-tight package with awetting composition applied to the wipe. The finished wipes may also bepackaged as a roll of separable sheets in a moisture-proof containerholding any desired number of sheets on the roll with a wettingcomposition applied to the wipes. The roll can be coreless and eitherhollow or solid. Coreless rolls, including rolls with a hollow center orwithout a solid center, can be produced with known coreless rollwinders, including those of SRP Industry, Inc. (San Jose, Calif.);Shimizu Manufacturing (Japan), and the devices disclosed in U.S. Pat.No. 4,667,890, issued May 26, 1987 to Gietman. Solid-wound corelessrolls can offer more product for a given volume and can be adapted for awide variety of dispensers.

[0089] Relative to the weight of the dry fabric, the wipe may desirablycontain from about 10 percent to about 400 percent of the wettingcomposition, more desirably from about 100 percent to about 300 percentof the wetting composition, and even more desirably from about 180percent to about 240 percent of the wetting composition. The wipemaintains its desired characteristics over the time periods involved inwarehousing, transportation, retail display and storage by the consumer.Accordingly, shelf life may range from two months to two years.

[0090] Various forms of impermeable envelopes and storage means forcontaining wet-packaged materials, such as wipes and towelettes and thelike, are well known in the art. Any of these may be employed inpackaging the pre-moistened wipes of the present invention.

[0091] Desirably, the pre-moistened wipes of the present invention arewetted with an aqueous wetting composition, which has one or more of thefollowing properties:

[0092] (1) is compatible with the above-described triggerable bindercompositions of the present invention;

[0093] (2) enables the pre-moistened wipe to maintain its wet strengthduring converting, storage and usage (including dispensing), as well as,dispersibility in a toilet bowl;

[0094] (3) does not cause skin irritation;

[0095] (4) reduces tackiness of the wipe, and provides unique tactileproperties, such as skin glide and a “lotion-like feel”; and

[0096] (5) acts as a vehicle to deliver “moist cleansing” and other skinhealth benefits.

[0097] The wetting composition should not act as a solvent for thebinder and generally does not contain solvents other than water, andparticularly does not contain organic solvents, though a small quantity(<1%) of a fragrance solubilizer, such as polysorbate 20, may bepresent, depending on the fragrance and the salt concentration of thewetting composition. Desirably, the wetting composition contains lessthan about 10 weight percent of organic solvents, such as propyleneglycol or other glycols, polyhydroxy alcohols, and the like, based onthe total weight of the wetting composition. More desirably, the wettingcomposition contains less than about 4 weight percent of organicsolvents. Even more desirably, the wetting composition contains lessthan about 1 weight percent of organic solvents. The wetting compositioncan be substantially free of organic solvents. By substantially free ismeant containing only a trivial or inconsequential amount, or an amountsuch that it has no effect on the triggerable property of the product.

[0098] One aspect of the present invention is a wetting composition,which contains an insolubilizing agent that maintains the strength of awater-dispersible binder until the insolubilizing agent is diluted withwater, whereupon the strength of the water-dispersible binder begins todecay. The water-dispersible binder may be any of the triggerable bindercompositions of the present invention or any other triggerable bindercomposition. The insolubilizing agent in the wetting composition can bea salt, such as those disclosed for the various triggerable polymers, ablend of salts having both monovalent and multivalent ions, or any othercompound, which provides in-use and storage strength to thewater-dispersible binder composition, and can be diluted in water topermit dispersion of the substrate as the binder polymer triggers to aweaker state. Desirably, the wetting composition contains more thanabout 2 weight percent of an insolubilizing agent based on the totalweight of the wetting composition for ion-sensitive polymers and morethan about 0.5 weight percent of an insolubilizing agent based on thetotal weight of the wetting composition for ion-specific polymers.Specifically, the wetting composition may contain from about 0.5 weightpercent to about 20 weight percent of an insolubilizing agentinsolubilizing agent. Even more specifically, the wetting compositionmay contain from about 1 weight percent to about 5 weight percent of aninsolubilizing agent. More precisely, the wetting composition maycontain from about 2 weight percent to about 4 weight percent of aninsolubilizing agent. A preferred blend of salts is NaCl and ZnCl₂.

[0099] The wetting composition of the present invention may furthercomprise a variety of additives compatible with the insolubilizing agentand the water-dispersible binder, such that the strength anddispersibility functions of the wipe are not jeopardized. Suitableadditives in the wetting composition include, but are not limited to,the following additives: skin-care additives; odor control agents;detackifying agents to reduce the tackiness of the binder; particulates;antimicrobial agents; preservatives; wetting agents and cleaning agents,such as detergents, surfactants, some silicones; emollients; surfacefeel modifiers for improved tactile sensation (e.g., lubricity) on theskin; fragrance; fragrance solubilizers; opacifiers; fluorescentwhitening agents; UV absorbers; pharmaceuticals; and pH control agents,such as malic acid or potassium hydroxide.

[0100] Skin-Care Additives

[0101] As used herein, the term “skin-care additives” representsadditives, which provide one or more benefits to the user, such as areduction in the probability of having diaper rash and/or other skindamage caused by fecal enzymes. These enzymes, particularly trypsin,chymotrypsin and elastase, are proteolytic enzymes produced in thegastrointestinal tract to digest food. In infants, for example, thefeces tend to be watery and contain, among other materials, bacteria,and some amounts of undegraded digestive enzymes. These enzymes, if theyremain in contact with the skin for any appreciable period of time, havebeen found to cause an irritation that is uncomfortable in itself andcan predispose the skin to infection by microorganisms. As acountermeasure, skin-care additives include, but are not limited to, theenzyme inhibitors and sequestrants set forth hereafter. The wettingcomposition may contain less than about 5 weight percent of skin-careadditives based on the total weight of the wetting composition. Morespecifically, the wetting composition may contain from about 0.01 weightpercent to about 2 weight percent of skin-care additives. Even morespecifically, the wetting composition may contain from about 0.01 weightpercent to about 0.05 weight percent of skin-care additives.

[0102] A variety of skin-care additives may be added to the wettingcomposition and the pre-moistened wipes of the present invention orincluded therein. In one embodiment of the present invention, skin-careadditives in the form of particles are added to serve as fecal enzymeinhibitors, offering potential benefits in the reduction of diaper rashand skin damage caused by fecal enzymes. U.S. Pat. No. 6,051,749, issuedApr. 18, 2000 to Schulz et al., the entirety of which is hereinincorporated by reference, discloses organophilic clays in a woven ornonwoven web, said to be useful for inhibiting fecal enzymes. Suchmaterials may be used in the present invention, including reactionproducts of a long chain organic quaternary ammonium compound with oneor more of the following clays: montmorillonite, bentonite, beidellite,hectorite, saponite, and stevensite.

[0103] Other known enzyme inhibitors and sequestrants may be used asskin-care additives in the wetting composition of the present invention,including those that inhibit trypsin and other digestive or fecalenzymes, and inhibitors for urease. For example, enzyme inhibitors andanti-microbial agents may be used to prevent the formation of odors inbody fluids. For example, urease inhibitors, which are also said to playa role in odor absorption, are disclosed by T. Trinh in World PatentApplication No. 98/26808, “Absorbent Articles with Odor Control System,”published Jun. 25, 1998, the entirety of which is herein incorporated byreference. Such inhibitors may be incorporated into the wettingcomposition and the pre-moistened wipes of the present invention andinclude transition metal ions and their soluble salts, such as silver,copper, zinc, ferric, and aluminum salts. The anion may also provideurease inhibition, such as borate, phytate, etc. Compounds of potentialvalue include, but are not limited to, silver chlorate, silver nitrate,mercury acetate, mercury chloride, mercury nitrate, copper metaborate,copper bromate, copper bromide, copper chloride, copper dichromate,copper nitrate, copper salicylate, copper sulfate, zinc acetate, zincborate, zinc phytate, zinc bromate, zinc bromide, zinc chlorate, zincchloride, zinc sulfate, cadmium acetate, cadmium borate, cadmiumbromide, cadmium chlorate, cadmium chloride, cadmium formate, cadmiumiodate, cadmium iodide, cadmium permanganate, cadmium nitrate, cadmiumsulfate, and gold chloride.

[0104] Other salts that have been disclosed as having urease inhibitionproperties include ferric and aluminum salts, especially the nitrates,and bismuth salts. Other urease inhibitors are disclosed by Trinh,including hydroxamic acid and its derivatives; thiourea; hydroxylamine;salts of phytic acid; extracts of plants of various species, includingvarious tannins, e.g. carob tannin, and their derivatives such aschlorogenic acid derivatives; naturally occurring acids such as ascorbicacid, citric acid, and their salts; phenyl phosphoro diamidate/diaminophosphoric acid phenyl ester; metal aryl phosphoramidate complexes,including substituted phosphorodiamidate compounds; phosphoramidateswithout substitution on the nitrogen; boric acid and/or its salts,including especially, borax, and/or organic boron acid compounds; thecompounds disclosed in European Patent Application 408,199; sodium,copper, manganese, and/or zinc dithiocarbamate; quinones; phenols;thiurams; substituted rhodanine acetic acids; alkylated benzoquinones;formamidine disulphide; 1:3-diketones maleic anhydride; succinamide;phthalic anhydride; pehenic acid; /N,N-dihalo-2-imidazolidinones;N-halo2-oxazolidinones; thio- and/or acyl-phosphoryltnamide and/orsubstituted derivatives thereof-, thiopyridine-N-oxides, thiopyridines,and thiopyrimidines; oxidized sulfur derivatives of diaminophosphinylcompounds; cyclotriphosphazatriene derivatives; ortho-diaminophosphinylderivatives of oximes; bromo-nitro compounds; S-aryl and/or alkyldiamidophosphorothiolates; diaminophosphinyl derivatives; mono- and/orpolyphosphorodiamide; 5-substituted-benzoxathiol-2-ones;N(diaminophosphinyl)arylcarboxamides; alkoxy- 1,2-benzothaizincompounds; etc.

[0105] Many other skin-care additives may be incorporated into thewetting composition and pre-moistened wipes of the present invention,including, but not limited to, sun blocking agents and UV absorbers,acne treatments, pharmaceuticals, baking soda (including encapsulatedforms thereof), vitamins and their derivatives such as Vitamins A or E,botanicals such as witch hazel extract and aloe vera, allantoin,emollients, disinfectants, hydroxy acids for wrinkle control oranti-aging effects, sunscreens, tanning promoters, skin lighteners,deodorants and anti-perspirants, ceramides for skin benefits and otheruses, astringents, moisturizers, nail polish removers, insectrepellants, antioxidants, antiseptics, anti-inflammatory agents and thelike, provided that the additives are compatible with an ion-sensitivebinder composition associated therewith, and especially theion-sensitive binder compositions of the present invention (i.e., theydo not cause a substantial loss of strength in the wet state of thepre-moistened wipes, prior to dilution in water, while permittingdispersibility in water).

[0106] Useful materials for skin care and other benefits are listed inMcCutcheon's 1999, Vol. 2: Functional Materials, M C Publishing Company,Glen Rock, N.J. Many useful botanicals for skin care are provided byActive Organics, Lewisville, Tex.

[0107] Odor Control Additives

[0108] Suitable odor control additives for use in the wettingcomposition and pre-moistened wipes of the present invention include,but are not limited to, zinc salts; talc powder; encapsulated perfumes(including microcapsules, macrocapsules, and perfume encapsulated inliposomes, vessicles, or microemulsions); chelants, such asethylenediamine tetra-acetic acid; zeolites; activated silica, activatedcarbon granules or fibers; activated silica particulates; polycarboxylicacids, such as citric acid; cyclodextrins and cyclodextrin derivatives;chitosan or chitin and derivatives thereof; oxidizing agents;antimicrobial agents, including silver-loaded zeolites (e.g., those of BF Technologies, located in Beverly, Mass., sold under the trademarkHEALTHSHIELD™); triclosan; kieselguhr; and mixtures thereof. In additionto controlling odor from the body or body wastes, odor controlstrategies can also be employed to mask or control any odor of thetreated substrate. Desirably, the wetting composition contains less thanabout 5 weight percent of odor control additives based on the totalweight of the wetting composition. More desirably, the wettingcomposition contains from about 0.01 weight percent to about 2 weightpercent of odor control additives. Even more desirably, the wettingcomposition contains from about 0.03 weight percent to about 1 weightpercent of odor control additives.

[0109] In one embodiment of the present invention, the wettingcomposition and/or pre-moistened wipes comprise derivatizedcyclodextrins, such as hydroxypropyl beta-cyclodextrin in solution,which remain on the skin after wiping and provide an odor-absorbinglayer. In other embodiments, the odor source is removed or neutralizedby application of an odor-control additive, exemplified by the action ofa chelant that binds metal groups necessary for the function of manyproteases and other enzymes that commonly produce an odor. Chelating themetal group interferes with the enzyme's action and decreases the riskof malodor in the product.

[0110] Principles for the application of chitosan or chitin derivativesto nonwoven webs and cellulosic fibers are described by S. Lee et al. in“Antimicrobial and Blood Repellent Finishes for Cotton and NonwovenFabrics Based on Chitosan and Fluoropolymers,” Textile Research Journal,69(2); 104-112, February 1999.

[0111] Detackifying Agents

[0112] While elevated salt concentrations may reduce the tack of thetriggerable binder, other means of tack reduction are often desirable.Thus, detackifying agents may be used in the wetting composition toreduce the tackiness, if any, of the triggerable binder. Suitabledetackifiers include any substance known in the art to reduce tackbetween two adjacent fibrous sheets treated with an adhesive-likepolymer or any substance capable of reducing the tacky feel of anadhesive-like polymer on the skin. Detackifiers may be applied as solidparticles in dry form, as a suspension or as a slurry of particles.Deposition may be by spray, coating, electrostatic deposition,impingement, filtration (i.e., a pressure differential drives aparticle-laden gas phase through the substrate, depositing particles bya filtration mechanism), and the like, and may be applied uniformly onone or more surfaces of the substrate or may be applied in a pattern(e.g., repeating or random patterns) over a portion of the surface orsurfaces of the substrate. The detackifier may be present throughout thethickness of the substrate, but may be concentrated at one or bothsurfaces, and may be substantially only present on one or both surfacesof the substrate.

[0113] Specific detackifiers include, but are not limited to, powders,such as talc powder, calcium carbonate, mica; starches, such as cornstarch; lycopodium powder; mineral fillers, such as titanium dioxide;silica powder; alumina; metal oxides in general; baking powder;kieselguhr; and the like. Polymers and other additives having lowsurface energy may also be used, including a wide variety of fluorinatedpolymers, silicone additives, polyolefins and thermoplastics, waxes,debonding agents known in the paper industry including compounds havingalkyl side chains such as those having 16 or more carbons, and the like.Compounds used as release agents for molds and candle making may also beconsidered, as well as, dry lubricants and fluorinated release agents.

[0114] In one embodiment, the detackifier comprisespolytetrafluorethylene (PTFE), such as PTFE telomer (KRYTOX® DF)compound, used in the PTFE release agent dry lubricant MS-122DF,marketed by Miller-Stephenson (Danbury, Conn.) as a spray product. Forexample, PTFE particles may be applied by spray to one side of thesubstrate prior to winding of the pre-moistened wipes. In oneembodiment, a detackifying agent is applied to only one surface of thesubstrate prior to winding into a roll.

[0115] The wetting composition desirably contains less than about 25weight percent of detackifying agents based on the total weight of thewetting composition. More desirably, the wetting composition containsfrom about 0.01 weight percent to about 10 weight percent ofdetackifying agents, more specifically about 5% or less. Even morespecifically, the wetting composition contains from about 0.05 weightpercent to about 2 weight percent of detackifying agents.

[0116] In addition to acting as a detackifying agent, starch compoundsmay also improve the strength properties of the pre-moistened wipes. Forexample, it has been found that ungelled starch particles, such ashydrophilic tapioca starch, when present at a level of about 1% orhigher by weight relative to the weight of the wetting composition, canpermit the pre-moistened wipe to maintain the same strength at a lowersalt concentration than is possible without the presence of starch.Thus, for example, a given strength can be achieved with 2% salt in thewetting composition in the presence of salt compared to a level of 4%salt being needed without starch. Starch may be applied by adding thestarch to a suspension of laponite to improve the dispersion of thestarch within the wetting composition.

[0117] Microparticulates

[0118] The wetting composition of the present invention may be furthermodified by the addition of solid particulates or microparticulates.Suitable particulates include, but are not limited to, mica, silica,alumina, calcium carbonate, kaolin, talc, and zeolites. The particulatesmay be treated with stearic acid or other additives to enhance theattraction or bridging of the particulates to the binder system, ifdesired. Also, two-component microparticulate systems, commonly used asretention aids in the papermaking industry, may also be used. Such twocomponent microparticulate systems generally comprise a colloidalparticle phase, such as silica particles, and a water-soluble cationicpolymer for bridging the particles to the fibers of the web to beformed. The presence of particulates in the wetting composition canserve one or more useful functions, such as (1) increasing the opacityof the pre-moistened wipes; (2) modifying the rheology or reducing thetackiness of the pre-moistened wipe; (3) improving the tactileproperties of the wipe; or (4) delivering desired agents to the skin viaa particulate carrier, such as a porous carrier or a microcapsule.Desirably, the wetting composition contains less than about 25 weightpercent of particulate based on the total weight of the wettingcomposition. More specifically, the wetting composition may contain fromabout 0.05 weight percent to about 10 weight percent ofmicroparticulate. Even more specifically, the wetting composition maycontain from about 0.1 weight percent to about 5 weight percent ofmicroparticulate.

[0119] Microcapsules and Other Delivery Vehicles

[0120] Microcapsules and other delivery vehicles may also be used in thewetting composition of the present invention to provide skin-careagents; medications; comfort promoting agents, such as eucalyptus;perfumes; skin care agents; odor control additives; vitamins; powders;and other additives to the skin of the user. Specifically, the wettingcomposition may contain up to about 25 weight percent of microcapsulesor other delivery vehicles based on the total weight of the wettingcomposition. More specifically, the wetting composition may contain fromabout 0.05 weight percent to about 10 weight percent of microcapsules orother delivery vehicles. Even more specifically, the wetting compositionmay contain from about 0.2 weight percent to about 5.0 weight percent ofmicrocapsules or other delivery vehicles.

[0121] Microcapsules and other delivery vehicles are well known in theart. For example, POLY-PORE® E200 (Chemdal Corp., Arlington Heights,Ill.), is a delivery agent comprising soft, hollow spheres that cancontain an additive at over 10 times the weight of the delivery vehicle.Known additives reported to have been used with POLY-PORE® E200 include,but are not limited to, benzoyl peroxide, salicylic acid, retinol,retinyl palmitate, octyl methoxycinnamate, tocopherol, siliconecompounds (DC 435), and mineral oil. Another useful delivery vehicle isa sponge-like material marketed as POLY-PORE® L200, which is reported tohave been used with silicone (DC 435) and mineral oil. Other knowndelivery systems include cyclodextrins and their derivatives, liposomes,polymeric sponges, and spray-dried starch.

[0122] Additives present in microcapsules are isolated from theenvironment and the other agents in the wetting composition until thewipe is applied to the skin, whereupon the microcapsules break anddeliver their load to the skin or other surfaces.

[0123] Preservatives and Anti-Microbial Agents

[0124] The wetting composition of the present invention may also containpreservatives and/or anti-microbial agents. Several preservatives and/oranti-microbial agents, such as Mackstat H 66 (available from McIntyreGroup, Chicago, Ill.), have been found to give excellent results inpreventing bacteria and mold growth. Other suitable preservatives andanti-microbial agents include, but are not limited to DMDM hydantoin(e.g., Glydant Plus™, Lonza, Inc., Fair Lawn, N.J.), iodopropynylbutylcarbamate, Kathon (Rohm and Hass, Philadelphia, Pa.),methylparaben, propylparaben, 2-bromo-2-nitropropane-1,3-diol, benzoicacid, and the like. Desirably, the wetting composition contains lessthan about 2 weight percent on an active basis of preservatives and/oranti-microbial agents based on the total weight of the wettingcomposition. More desirably, the wetting composition contains from about0.01 weight percent to about 1 weight percent of preservatives and/oranti-microbial agents. Even more desirably, the wetting compositioncontains from about 0.01 weight percent to about 0.5 weight percent ofpreservatives and/or anti-microbial agents.

[0125] Wetting Agents and Cleaning Agents

[0126] A variety of wetting agents and/or cleaning agents may be used inthe wetting composition of the present invention. Suitable wettingagents and/or cleaning agents include, but are not limited to,detergents and nonionic, amphoteric, and anionic surfactants, especiallyamino acid-based surfactants. Amino acid-based surfactant systems, suchas those derived from amino acids L-glutamic acid and other naturalfatty acids, offer pH compatibility to human skin and good cleansingpower, while being relatively safe and providing improved tactile andmoisturization properties compared to other anionic surfactants. Onefunction of the surfactant is to improve wetting of the dry substratewith the wetting composition. Another function of the surfactant can beto disperse bathroom soils when the pre-moistened wipe contacts a soiledarea and to enhance their absorption into the substrate. The surfactantcan further assist in make-up removal, general personal cleansing, hardsurface cleansing, odor control, and the like.

[0127] One commercial example of an amino-acid based surfactant isacylglutamate, marketed under the Amisoft name by Ajinomoto Corp.,Tokyo, Japan. Desirably, the wetting composition contains less thanabout 3 weight percent of wetting agents and/or cleaning agents based onthe total weight of the wetting composition. More desirably, the wettingcomposition contains from about 0.01 weight percent to about 2 weightpercent of wetting agents and/or cleaning agents. Even more desirably,the wetting composition contains from about 0.1 weight percent to about0.5 weight percent of wetting agents and/or cleaning agents.

[0128] Although amino-acid based surfactants are particularly useful inthe wetting compositions of the present invention, a wide variety ofsurfactants may be used in the present invention. Suitable non-ionicsurfactants include, but are not limited to, the condensation productsof ethylene oxide with a hydrophobic (oleophilic) polyoxyalkylene baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds desirably has a molecular weightsufficiently high so as to render it water-insoluble. The addition ofpolyoxyethylene moieties to this hydrophobic portion increases thewater-solubility of the molecule as a whole, and the liquid character ofthe product is retained up to the point where the polyoxyethylenecontent is about 50% of the total weight of the condensation product.Examples of compounds of this type include commercially-availablePluronic surfactants (BASF Wyandotte Corp.), especially those in whichthe polyoxypropylene ether has a molecular weight of about 1500-3000 andthe polyoxyethylene content is about 35-55% of the molecule by weight,i.e. Pluronic L-62.

[0129] Other usefuil nonionic surfactants include, but are not limitedto, the condensation products of C₈-C₂₂ alkyl alcohols with 2-50 molesof ethylene oxide per mole of alcohol. Examples of compounds of thistype include the condensation products of C₁₁-C₁₅ secondary alkylalcohols with 3-50 moles of ethylene oxide per mole of alcohol, whichare commercially-available as the Poly-Tergent SLF series from OlinChemicals or the TERGITOL® series from Union Carbide; i.e., TERGITOL®25-L-7, which is formed by condensing about 7 moles of ethylene oxidewith a C₁₂-C₁₅ alkanol.

[0130] Other nonionic surfactants, which may be employed in the wettingcomposition of the present invention, include the ethylene oxide estersof C₆-C₁₂ alkyl phenols such as (nonylphenoxy)polyoxyethylene ether.Particularly usefuil are the esters prepared by condensing about 8-12moles of ethylene oxide with nonylphenol, i.e. the IGEPAL® CO series(GAF Corp.).

[0131] Further non-ionic surface active agents include, but are notlimited to, alkyl polyglycosides (APG), derived as a condensationproduct of dextrose (D-glucose) and a straight or branched chainalcohol. The glycoside portion of the surfactant provides a hydrophilehaving high hydroxyl density, which enhances water solubility.Additionally, the inherent stability of the acetal linkage of theglycoside provides chemical stability in alkaline systems. Furthermore,unlike some non-ionic surface active agents, alkyl polyglycosides haveno cloud point, allowing one to formulate without a hydrotrope, andthese are very mild, as well as readily biodegradable non-ionicsurfactants. This class of surfactants is available from HorizonChemical under the trade names of APG-300, APG-350, APG-500, andAPG-500.

[0132] Silicones are another class of wetting agents available in pureform, or as microemulsions, macroemulsions, and the like. One exemplarynon-ionic surfactant group is the silicone-glycol copolymers. Thesesurfactants are prepared by adding poly(lower)alkylenoxy chains to thefree hydroxyl groups of dimethylpolysiloxanols and are available fromthe Dow Coming Corp as Dow Coming 190 and 193 surfactants (CTFA name:dimethicone copolyol). These surfactants function, with or without anyvolatile silicones used as solvents, to control foaming produced by theother surfactants, and also impart a shine to metallic, ceramic, andglass surfaces.

[0133] Anionic surfactants may also be used in the wetting compositionsof the present invention. Anionic surfactants are useful due to theirhigh detergency include anionic detergent salts having alkylsubstituents of 8 to 22 carbon atoms such as the water-soluble higherfatty acid alkali metal soaps, e.g., sodium myristate and sodiumpalmitate. A preferred class of anionic surfactants encompasses thewater-soluble sulfated and sulfonated anionic alkali metal and alkalineearth metal detergent salts containing a hydrophobic higher alkyl moiety(typically containing from about 8 to 22 carbon atoms) such as salts ofhigher alkyl mono or polynuclear aryl sulfonates having from about 1 to16 carbon atoms in the alkyl group, with examples available as theBio-Soft series, i.e. Bio-Soft D-40 (Stepan Chemical Co.).

[0134] Other useful classes of anionic surfactants include, but are notlimited to, the alkali metal salts of alkyl naphthalene sulfonic acids(methyl naphthalene sodium sulfonate, Petro AA, PetrochemicalCorporation); sulfated higher fatty acid monoglycerides such as thesodium salt of the sulfated monoglyceride of cocoa oil fatty acids andthe potassium salt of the sulfated monoglyceride of tallow fatty acids;alkali metal salts of sulfated fatty alcohols containing from about 10to 18 carbon atoms (e.g., sodium lauryl sulfate and sodium stearylsulfate); sodium C₁₄-C₁₆ -alphaolefin sulfonates such as the Bio-Tergeseries (Stepan Chemical Co.); alkali metal salts of sulfated ethyleneoxyfatty alcohols (the sodium or ammonium sulfates of the condensationproducts of about 3 moles of ethylene oxide with a C₁₂-C₁₅ n-alkanol;i.e., the Neodol ethoxysulfates, Shell Chemical Co.); alkali metal saltsof higher fatty esters of low molecular weight alkylol sulfonic acids,e.g. fatty acid esters of the sodium salt of isothionic acid, the fattyethanolamide sulfates; the fatty acid amides of amino alkyl sulfonicacids; e.g., lauric acid amide of taurine; as well as numerous otheranionic organic surface active agents such as sodium xylene sulfonate,sodium naphthalene sulfonate, sodium toulene sulfonate and mixturesthereof.

[0135] A further useful class of anionic surfactants includes the8-(4-n-alkyl-2-cyclohexenyl)-octanoic acids, wherein the cyclohexenylring is substituted with an additional carboxylic acid group. Thesecompounds or their potassium salts, are commercially-available fromWestvaco Corporation as Diacid 1550 or H-240. In general, these anionicsurface active agents can be employed in the form of their alkali metalsalts, ammonium or alkaline earth metal salts.

[0136] Macroemulsions and Microemulsion of Silicone Particles

[0137] The wetting composition may further comprise an aqueousmicroemulsion of silicone particles. For example, U.S. Pat. No.6,037,407, “Process for the Preparation of Aqueous Emulsions of SiliconeOils and/or Gums and/or Resins” issued Mar. 14, 2000, disclosesorganopolysiloxanes in an aqueous microemulsion. Desirably, the wettingcomposition contains less than about 5 weight percent of a microemulsionof silicone particles based on the total weight of the wettingcomposition. More desirably, the wetting composition contains from about0.02 weight percent to about 3 weight percent of a microemulsion ofsilicone particles. Even more desirably, the wetting compositioncontains from about 0.02 weight percent to about 0.5 weight percent of amicroemulsion of silicone particles.

[0138] Silicone emulsions in general may be applied to the pre-moistenedwipe by any known coating method. For example, the pre-moistened wipemay be moistened with an aqueous composition comprising awater-dispersible or water-miscible, silicone-based component that iscompatible with the insolubilizing compound in the wetting composition.Further, the wipe can comprise a nonwoven web of fibers having awater-dispersible binder, wherein the web is moistened with a lotioncomprising a silicone-based sulfosuccinate. The silicone-basedsulfosuccinate provides gentle and effective cleansing without a highlevel of surfactant. Additionally, the silicone-based sulfosuccinateprovides a solubilization function, which prevents precipitation ofoil-soluble components, such as fragrance components, vitamin extracts,plant extracts, and essential oils.

[0139] In one embodiment of the present invention, the wettingcomposition comprises a silicone copolyol sulfosuccinate, such asdisodium dimethicone copolyol sulfosuccinate and diammonium dimethiconecopolyolsulfosuccinate. Desirably, the wetting composition comprisesless than about 2 percent by weight of the silicone-basedsulfosuccinate, and more desirably from about 0.05 percent to about 0.30percent by weight of the silicone-based sulfosuccinate.

[0140] In another example of a product comprising a silicone emulsions,Dow Coming 9506 powder may also be present in the wetting composition.Dow Coming 9506 powder is believed to comprise adimethicone/vinyldimethicone cross-polymer and is a spherical powder,which is said to be useful in controlling skin oils (see “New ChemicalPerspectives,” Soap and Cosmetics, Vol. 76, No. 3, March 2000, p. 12).Thus, a water-dispersible wipe, which delivers a powder effective incontrolling skin oil, is also within the scope of the present invention.Principles for preparing silicone emulsions are disclosed in WO97/10100, published Mar. 20, 1997.

[0141] Emollients

[0142] The wetting composition of the present invention may also containone or more emollients. Suitable emollients include, but are not limitedto, PEG 75 lanolin, methyl gluceth 20 benzoate, C₁₂-C₁₅ alkyl benzoate,ethoxylated cetyl stearyl alcohol, products marketed as Lambent waxWS-L, Lambent W D-F, Cetiol H E (Henkel Corp.), Glucam P20 (Amerchol),Polyox WSR N-10 (Union Carbide), Polyox WSR N-3000 (Union Carbide),Luviquat (BASF), Finsolv SLB 101 (Finetex Corp.), mink oil, allantoin,stearyl alcohol, Estol 1517 (Unichema), and Finsolv SLB 201 (FinetexCorp.).

[0143] An emollient can also be applied to a surface of the articleprior to or after wetting with the wetting composition. Such anemollient may be insoluble in the wetting composition and can beimmobile except when exposed to a force. For example, a petrolatum-basedemollient can be applied to one surface in a pattern, after which theother surface is wetted to saturate the wipe. Such a product couldprovide a cleaning surface and an opposing skin treatment surface.

[0144] The emollient composition in such products and other products ofthe present invention can comprise a plastic or fluid emollient such asone or more liquid hydrocarbons (e.g., petrolatum), mineral oil and thelike, vegetable and animal fats (e.g., lanolin, phospholipids and theirderivatives) and/or a silicone materials such as one or more alkylsubstituted polysiloxane polymers, including the polysiloxane emollientsdisclosed in U.S. Pat. No. 5,891,126, issued Apr. 6, 1999 to Osborn, IIIet al. Optionally, a hydrophilic surfactant may be combined with aplastic emollient to improve wettability of the coated surface. In someembodiments of the present invention, it is contemplated that liquidhydrocarbon emollients and/or alkyl substituted polysiloxane polymersmay be blended or combined with one or more fatty acid ester emollientsderived from fatty acids or fatty alcohols.

[0145] In an embodiment of the present invention, the emollient materialis in the form of an emollient blend. Desirably, the emollient blendcomprises a combination of one or more liquid hydrocarbons (e.g.,petrolatum), mineral oil and the like, vegetable and animal fats (e.g.,lanolin, phospholipids and their derivatives), with a silicone materialsuch as one or more alkyl substituted polysiloxane polymers. Moredesirably, the emollient blend comprises a combination of liquidhydrocarbons (e.g., petrolatum) with dimethicone or with dimethicone andother alkyl substituted polysiloxane polymers. In some embodiments ofthe present invention, it is contemplated that blends of liquidhydrocarbon emollients and/or alkyl substituted polysiloxane polymersmay be blended with one or more fatty acid ester emollients derived fromfatty acids or fatty alcohols. PEG-7 glyceryl cocoate, available asStandamul HE (Henkel Corp., Hoboken, N.J.), can also be considered.

[0146] Water-soluble, self-emulsifying emollient oils, which are usefulin the present wetting compositions, include the polyoxyalkoxylatedlanolins and the polyoxyalkoxylated fatty alcohols, as disclosed in U.S.Pat. No. 4,690,821, issued Sep. 1, 1987 to Smith et al. Thepolyoxyalkoxy chains desirably will comprise mixed propylenoxy andethyleneoxy units. The lanolin derivatives will typically comprise about20-70 such lower-alkoxy units while the C₁₂-C₂₀—fatty alcohols will bederivatized with about 8-15 lower- alkyl units. One such useful lanolinderivative is Lanexol AWS (PPG-12-PEG-50, Croda, Inc., New York, N.Y.).A useful poly(15-20)C₂-C₃-alkoxylate is PPG-5-Ceteth-20, known asProcetyl AWS (Croda, Inc.).

[0147] According to one embodiment of the present invention, theemollient material reduces undesirable tactile attributes, if any, ofthe wetting composition. For example, emollient materials, includingdimethicone, can reduce the level of tackiness that may be caused by theion-sensitive binder or other components in the wetting composition,thus serving as a detackifier.

[0148] Desirably, the wetting composition contains less than about 25weight percent of emollients based on the total weight of the wettingcomposition. More specifically, the wetting composition may compriseless than about 5 weight percent emollient, and most specifically lessthan about 2% emollient. More desirably, the wetting composition maycontain from about 0.01 weight percent to about 8 weight percent ofemollients. Even more desirably, the wetting composition may containfrom about 0.2 weight percent to about 2 weight percent of emollients.

[0149] In one embodiment, the wetting composition and/or pre-moistenedwipes of the present invention comprise an oil-in-water emulsioncomprising an oil phase containing at least one emollient oil and atleast one emollient wax stabilizer dispersed in an aqueous phasecomprising at least one polyhydric alcohol emollient and at least oneorganic water-soluble detergent, as disclosed in U.S. Pat. No.4,559,157, issued Dec. 17, 1985 to Smith et al., the entirety of whichis herein incorporated by reference.

[0150] Surface Feel Modifiers

[0151] Surface feel modifiers are used to improve the tactile sensation(e.g., lubricity) of the skin during use of the product. Suitablesurface feel modifiers include, but are not limited to, commercialdebonders; and softeners, such as the softeners used in the art oftissue making including quaternary ammonium compounds with fatty acidside groups, silicones, waxes, and the like. Exemplary quaternaryammonium compounds with utility as softeners are disclosed in U.S. Pat.No. 3,554,862, issued to Hervey et al. on Jan. 12, 1971; U.S. Pat. No.4,144,122, issued to Emanuelsson et al., Mar. 13, 1979, U.S. Pat. No.5,573,637, issued to Ampulski et al. Nov. 12, 1996; and U.S. Pat. No.4,476,323, issued to Hellsten et al., Oct. 9, 1984, the entirety of allof which is herein incorporated by reference. Desirably, the wettingcomposition contains less than about 2 weight percent of surface feelmodifiers based on the total weight of the wetting composition. Moredesirably, the wetting composition contains from about 0.01 weightpercent to about 1 weight percent of surface feel modifiers. Even moredesirably, the wetting composition contains from about 0.01 weightpercent to about 0.05 weight percent of surface feel modifiers.

[0152] Fragrances

[0153] A variety of fragrances may be used in the wetting composition ofthe present invention. Desirably, the wetting composition contains lessthan about 2 weight percent of fragrances based on the total weight ofthe wetting composition. More desirably, the wetting compositioncontains from about 0.01 weight percent to about 1 weight percent offragrances. Even more desirably, the wetting composition contains fromabout 0.01 weight percent to about 0.05 weight percent of fragrances.

[0154] Fragrance Solubilizers

[0155] Further, a variety of fragrance solubilizers may be used in thewetting composition of the present invention. Suitable fragrancesolubilizers include, but are not limited to, polysorbate 20, propyleneglycol, ethanol, isopropanol, diethylene glycol monoethyl ether,dipropylene glycol, diethyl phthalate, triethyl citrate, Ameroxol OE-2(Amerchol Corp.), Brij 78 and Brij 98 (ICI Surfactants), Arlasolve 200(ICI Surfactants), Calfax 16L-35 (Pilot Chemical Co.), Capmul POE-S(Abitec Corp.), Finsolv SUBSTANTIAL (Finetex), and the like. Desirably,the wetting composition contains less than about 2 weight percent offragrance solubilizers based on the total weight of the wettingcomposition. More desirably, the wetting composition contains from about0.01 weight percent to about 1 weight percent of fragrance solubilizers.Even more desirably, the wetting composition contains from about 0.01weight percent to about 0.05 weight percent of fragrance solubilizers.

[0156] Opacifiers

[0157] Suitable opacifiers include, but are not limited to, titaniumdioxide or other minerals or pigments, and synthetic opacifiers, such asREACTOPAQUE® particles (available from Sequa Chemicals, Inc., Chester,S.C.). Desirably, the wetting composition contains less than about 2weight percent of opacifiers based on the total weight of the wettingcomposition. More desirably, the wetting composition contains from about0.01 weight percent to about 1 weight percent of opacifiers. Even moredesirably, the wetting composition contains from about 0.01 weightpercent to about 0.05 weight percent of opacifiers.

[0158] pH Control Agents

[0159] Suitable pH control agents for use in the wetting composition ofthe present invention include, but are not limited to, hydrochloricacid, acetic acid, sodium hydroxide, potassium hydroxide, and the like.An appropriate pH range minimizes the amount of skin irritationresulting from the wetting composition on the skin. Desirably, the pHrange of the wetting composition is from about 3.5 to about 6.5. Moredesirably, the pH range of the wetting composition is from about 4 toabout 6. Desirably the overall pH of the wet wipe product; i.e., thecomplete wet wipe product including the fabric portion and the wettingsolution portion, is from about 3.9-4.5; preferably, about 4.2.Desirably, the wetting composition contains less than about 2 weightpercent of a pH adjuster based on the total weight of the wettingcomposition. More desirably, the wetting composition contains from about0.01 weight percent to about 1 weight percent of a pH adjuster. Evenmore desirably, the wetting composition contains from about 0.01 weightpercent to about 0.05 weight percent of a pH adjuster.

[0160] Although a variety of wetting compositions, formed from one ormore of the above-described components, may be used with the wet wipesof the present invention, in one embodiment, the wetting compositioncontains the following components, given in weight percent of thewetting composition, as shown in Table 2 below: TABLE 2 WettingComposition Components Wetting Composition Component: Weight Percent:Deionized Water about 86 to about 98 Insolubilizing compound about 2 toabout 20 Preservative Up to about 2 Surfactant Up to about 2 SiliconeEmulsion Up to about 1 Emollient Up to about 1 Fragrance Up to about 0.3Fragrance solubilizer Up to about 0.5 pH adjuster Up to about 0.2

[0161] In another embodiment of the present invention, the wettingcomposition comprises the following components, given in weight percentof the wetting composition, as shown in Table 3 below: TABLE 3 WettingComposition Components Class of Wetting Specific Wetting CompositionComposition Component Weight Component: Component: Name: Percent:Vehicle Deionized Water about 86 to about 98 Insolubilizing SodiumChloride about 2 to compound (Millport Ent., about 20 Milwaukee, WI)Preservative Glycerin, IPBC and Mackstat H-66 Up to about DMDM Hydantoin(McIntyre 2 Group, Chicago, IL) Surfactant Acyl Glutamate CS22 Up toabout (Ajinomoto, 2 Tokyo, Japan) Silicone Dimethiconol and DC1785 Up toabout Emulsion TEA Dodecylbenezene (Dow Corning, 1 (Detackifier/SkSulfonate Midland, MI) in Feel agent) Emollient PEG-75 Lanolin SolulanL-575 Up to about (Amerchol, 1 Middlesex, NJ) Fragrance FragranceDragoco Up to about 0/708768 0.3 (Dragoco, Roseville, MN) FragrancePolysorbate 20 Glennsurf L20 Up to about solubilizer (Glenn Corp., St.0.5 Paul, MN) pH adjuster Malic Acid to pH 5 Up to about (Haarman &Reimer, 0.2 Tetrboro,NJ)

[0162] In another embodiment of the present invention, the wettingcomposition comprises the following components, given in weight percentof the wetting composition, as shown in Table 4 below: TABLE 4 AnExemplary Wetting Composition Class of Wetting Specific Wettingcomposition composition Component Component: Component: Name: WeightPercent: Vehicle Deionized Water about 93 Insolubilizing Zinc Chlorideabout 1 compound Preservative Glycerin, IPBC and Mackstat about 1 DMDMHydantoin H-66 Surfactant Acyl Glutamate CS22/ECS about 1 22P SiliconeDimethiconol and DC 1784/ about 0.5 Emulsion TEA DC 1785 DodecylbenezeneSulfonate Emollient PEG-75 Lanolin Solulan L-575 about 0.25 FragranceFragrance Dragoco about 0.05 Fragrance 0/708768 Fragrance Polysorbate 20Glennsurf L20 about 0.25 solubilizer pH adjuster Malic Acid to pH 5about 0.07

[0163] It should be noted that the above-described wetting compositionsof the present invention may be used with any one of the above-describedtriggerable binder compositions of the present invention. Further, theabove-described wetting compositions of the present invention may beused with any other binder composition, including conventional bindercompositions, or with any known fibrous or absorbent substrate, whetherdispersible or not.

[0164] Strength Properties

[0165] In one embodiment of the present invention, wet wipes areproduced using the above-described wetting composition in Table 3 and anair-laid fibrous material comprising about 80 weight percent of bleachedkraft fibers and 20 weight percent of any of the above-describedion-specific binder compositions of the present invention, wherein theweight percentages are based on the total weight of the dry nonwovenfabric. In a further embodiment of the present invention, wet wipes areproduced using the above-described wetting composition in Table 2 and anair-laid fibrous material comprising 90 weight percent of softwoodfibers and 10 weight percent of an ion-sensitive binder of the presentinvention. The amount of wetting composition added to the nonwovenfabric, relative to the weight of the dry nonwoven fabric in theseembodiments, is desirably about 180 percent to about 240 weight percent.

[0166] Desirably, the wet wipes of the present invention possess anin-use wet tensile strength cross deckle wet tensile (CDWT) of at leastabout 100 g/in, and a tensile strength of less than about 30 g/in afterbeing soaked in water having a concentration of Ca²⁺ and/or Mg²⁺ ions ofabout 50 ppm for about one hour. More desirably, the wet wipes possessan in-use wet tensile strength of at least about 300 g/in (CDWT), and atensile strength of less than about 20 g/in after being soaked in waterhaving a concentration of Ca²⁺ and/or Mg²⁺ ions of about 50 ppm forabout one hour. In a further embodiment, the wet wipes desirably possessan in-use wet tensile strength of at least about 100 g/in (CDWT), and atensile strength of less than about 30 g/in after being soaked in waterhaving a concentration of Ca²⁺ and/or Mg²⁺ ions of about 200 ppm forabout one hour. Even more desirably, the wet wipes possess an in-use wettensile strength of at least about 300 g/in (CDWT), and a tensilestrength of less than about 20 g/in after being soaked in water having aconcentration of Ca²⁺ and/or Mg²⁺ ions of about 200 ppm for about onehour.

[0167] Desirably, the wet wipes treated with the binder material of thepresent invention possess an in-use wet tensile strength of at least 100g/in for a 1 inch width sample in the cross machine direction whensoaked with 10% to 400% by weight wet wipes solution containing morethan 2% by weight monovalent ion (NaCl) concentration and a tensilestrength of less than about 30 g/in after being soaked in deionizedwater for about one hour. More desirably, the wet wipes treated with thebinder material of the present invention possess an in-use tensilestrength of at least 200 g/in for a 1 inch width sample in the crossmachine direction when soaked with 10% to 400% by weight wet wipessolution containing more than 2% by weight monovalent ion (NaCl)concentration and a tensile strength of less than about 30 g/in afterbeing soaked in deionized water for about one hour. More desirably, thewet wipes treated with the binder material of the present inventionpossess an in-use tensile strength of at least 300 g/in for a 1 inchwidth sample in the cross machine direction when soaked with 10% to 400%by weight wet wipes solution containing more than 2% by weightmonovalent ion (NaCl) concentration and a tensile strength of less thanabout 20 g/in after being soaked in deionized water for about one hour.

[0168] Desirably, the wet wipes treated with the binder material of thepresent invention possess an in-use wet tensile strength of at least 100g/in for a 1 inch width sample in the cross machine direction whensoaked with 10% to 400% by weight wet wipes solution containing morethan 0.5% by weight ZnCl₂ and a tensile strength of less than about 30g/in after being soaked in deionized water for about one hour. Moredesirably, the wet wipes treated with the binder material of the presentinvention possess an in-use tensile strength of at least 200 g/in for a1 inch width sample in the cross machine direction when soaked with 10%to 400% by weight wet wipes solution containing more than 0.5% by weightZnCl₂ and a tensile strength of less than about 30 g/in after beingsoaked in deionized water for about one hour. More desirably, the wetwipes treated with the binder material of the present invention possessan in-use tensile strength of at least 300 g/in for a 1 inch widthsample in the cross machine direction when soaked with 10% to 400% byweight wet wipes solution containing more than 0.5% by weight ZnCl₂ anda tensile strength of less than about 20 g/in after being soaked indeionized water for about one hour.

[0169] Products with high basis weights or wet strengths than flushablewet wipes may have relatively higher wet tensile strength. For example,products, such as pre-moistened towels or hard-surface cleaning wipes,may have basis weights above 70 gsm, such as from 80 gsm to 150 gsm.Such products can have CDWT values of 500 g/in or greater, and aftersoaking values of about 150 g/in or less, more specifically about 100g/in or less, and most specifically about 50 g/in or less.

[0170] Method of Making Wet Wipes

[0171] The pre-moistened wipes of the present invention can be made inseveral ways. In one embodiment, the triggerable polymer composition isapplied to a fibrous substrate as part of an aqueous solution orsuspension, wherein subsequent drying is needed to remove the water andpromote binding of the fibers. In particular, during drying, the bindermigrates to the crossover points of the fibers and becomes activated asa binder in those regions, thus providing acceptable strength to thesubstrate. For example, the following steps can be applied:

[0172] 1. Providing an absorbent substrate that is not highly bonded(e.g., an unbonded airlaid, a tissue web, a carded web, fluff pulp,etc.).

[0173] 2. Applying a triggerable polymer composition to the substrate,typically in the form of a liquid, suspension, or foam.

[0174] 3. Drying the substrate to promote bonding of the substrate. Thesubstrate may be dried such that the peak substrate temperature does notexceed about 100° to 220° C. In one embodiment, the substratetemperature does not exceed 60° C. to 80° C.

[0175] 5. Applying a wetting composition to the substrate.

[0176] 6. Placing the wetted substrate in roll form or in a stack andpackaging the product.

[0177] Application of the triggerable polymer composition to thesubstrate can be by means of spray; by foam application; by immersion ina bath; by curtain coating; by coating and metering with a wire-woundrod; by passage of the substrate through a flooded nip; by contact witha pre-metered wetted roll coated with the binder solution; by pressingthe substrate against a deformable carrier containing the triggerablepolymer composition such as a sponge or felt to effect transfer into thesubstrate; by printing such as gravure, inkjet, or flexographicprinting; and any other means known in the art.

[0178] In the use of foams to apply a binder or co-binder polymer, themixture is frothed, typically with a foaming agent, and spread uniformlyon the substrate, after which vacuum is applied to pull the froththrough the substrate. Any known foam application method can be used,including that of U.S. Pat. No. 4,018,647, “Process for the Impregnationof a Wet Fiber Web with a Heat Sensitized Foamed Latex Binder,” issuedApr. 19, 1977 to Wietsma, the entirety of which is herein incorporatedby reference. Wietsma discloses a method wherein a foamed latex isheat-sensitized by the addition of a heat-sensitizer such as functionalsiloxane compounds including siloxane oxyalkylene block copolymers andorganopolysiloxanes. Specific examples of applicable heat-sensitizersand their use thereof for the heat sensitization of latices aredescribed in the U.S. Pat. Nos. 3,255,140; 3,255,141; 3,483,240 and3,484,394, all of which are incorporated herein by reference. The use ofa heat-sensitizer is said to result in a product having a very soft andtextile-like hand compared to prior methods of applying foamed latexbinders.

[0179] The amount of heat-sensitizer to be added is dependent on, interalia, the type of latex used, the desired coagulation temperature, themachine speed and the temperatures in the drying section of the machine,and will generally be in the range of about 0.05 to about 3% by weight,calculated as dry matter on the dry weight of the latex; but also largeror smaller amounts may be used. The heat sensitizer can be added in suchan amount that the latex will coagulate far below the boiling point ofwater, for instance at a temperature in the range of 35° C. to 95° C.,or from about 35° C. to 65° C.

[0180] Without wishing to be bound by theory, it is believed that adrying step after application of the triggerable binder solution andbefore application of the wetting composition enhances bonding of afibrous substrate by driving the binder to fiber crossover points asmoisture is driven off, thus promoting efficient use of the binder.However, in an alternative method, the drying step listed above isskipped, and the triggerable polymer composition is applied to thesubstrate followed by application of the wetting composition withoutsignificant intermediate drying. In one version of this method, thetriggerable polymer composition selectively adheres to the fibers,permitting excess water to be removed in an optional pressing stepwithout a significant loss of the binder from the substrate. In anotherversion, no significant water removal occurs prior to application of thewetting composition. In yet another alternative method, the triggerablepolymer composition and the wetting composition are appliedsimultaneously, optionally with subsequent addition of salt or otherinsolubilizing compounds to further render the binder insoluble.

[0181] The present invention is further illustrated by the followingexamples, which are not to be construed in any way as imposinglimitations upon the scope thereof. On the contrary, it is to be clearlyunderstood that resort may be had to various other embodiments,modifications, and equivalents thereof which, after reading thedescription herein, may suggest themselves to those skilled in the artwithout departing from the spirit of the present invention and/or thescope of the appended claims.

[0182] As used herein, the “thickness” of a web is measured with a 3-inacrylic plastic disk connected to the spindle of a Mitutoyo DigimaticIndicator (Mitutoyo Corporation, 31-19, Shiba 5-chome, Minato-ku, Tokyo108, Japan) and which delivers a net load of 0.05 psi to the samplebeing measured. The Mitutoyo Digimatic Indicator is zeroed when the diskrests on a flat surface. When a sample having a size at least as greatas the acrylic disk is placed under the disk, a thickness reading can beobtained from the digital readout of the indicator. Water-dispersiblesubstrates of the present invention can have any suitable thickness,such as from about 0.1 mm to 5 mm. For wet wipes, thicknesses can be inthe range of 0.2 mm to about 1 mm, more specifically from about 0.3 mmto about 0.7 mm. Thickness can be controlled, for example, by theapplication of compaction rolls during or after web formation, bypressing after binder or wetting composition has been applied, or bycontrolling the tension of winding when forming a roll good.

[0183] The use of the platen method to measure thickness gives anaverage thickness at the macroscopic level. Local thickness may vary,especially if the product has been embossed or has otherwise been givena three-dimensional texture.

EXAMPLE 1

[0184] Polymers were synthesized by free radical polymerization ofvarying combinations of the following monomers: acrylic acid,acrylamide, butyl acrylate, 2-ethylhexyl acrylate and[2(methacryloyloxy)ethyl] trimethyl ammonium chloride (“MQUAT”). Eachpolymerization was conducted in methanol. A typical procedure is statedbelow.

[0185] Acrylamide (39.1 g, 0.55 mol), butyl acrylate (32.0 g, 0.25 mol),2-ethylhexyl acrylate (18.4 g, 0.10 mol), and MQUAT (27.6 g of 75 wt %solution, 0.10 mol) were dissolved in 50 g of methanol. A free radicalinitiator, 2,2″Azobisisobutyronitrile (“AIBN”) (0.66 g, 4.0×10″ mol) wasdissolved in 20 ml of methanol. The monomer solution was deoxygenated bybubbling N₂ through the solution for 20 minutes. To a 1000 ml roundbottom, three neck flask equipped with a condenser, two addition funnelsand a magnetic stirrer was added 125 g of methanol. The solvent washeated to gentle reflux under nitrogen. Monomers and initiator wereadded simultaneously from the addition funnels over a period of twohours. Polymerization was allowed to proceed for an additional twohours, at the end of which the addition funnels and condenser werereplaced with a distillation head and a mechanical stir rod to removemethanol. A steady stream of N₂ was maintained during distillation. Whenthe distillation was completed (about 3 hours), 400 g of deionized waterwas added to the polymer solution. The heat was removed and the solutionwas allowed to stir overnight.

[0186] Alternatively, the polymers can be made by adding the monomersand initiator to the reaction flask all at once and reacting for fourhours. This synthesis method is referred as “one pot” synthesis in thesubsequent section. A total of eight polymers were synthesized and theircompositions are summarized in Table 5 below. TABLE 5 PolymerComposition Sample % MQUAT % AM % AA % BA % EHA 1 10 0 55 25 10 2 10 550 25 10 3 60 0 0 20 20 4 45 0 0 35 20 5 35 0 0 35 30 6 30 0 0 35 35 7 200 0 40 40 8 15 0 0 45 40

[0187] Sample Preparation

[0188] A water-dispersible, wet-laid nonwoven composed of BFF rayonfibers (1.5 d×25 mm) was utilized as the base sheet for testing. Eachbase sheet was cut to an approximate size of 5.5 in (CD)×9 in (MD). Apiece of release paper was placed onto a notepad, followed by a basesheet. Both pieces were taped to the notepad with a single piece ofScotch tape. A #20 grooved, wire-wound rod was laid across the top ofthe sample. A strip of the polymer solution to be tested was pouredalong the rod. The rod was then rolled down the length of the sample,with gentle pressure applied. Excess polymer was wiped off the bottom ofthe release paper, and the sample was placed into a forced air oven at60° C. for at least 10 minutes. The rod was cleaned between each sampleas necessary. Once the samples were dry, they were removed from theoven. The top part of each sample was removed with a paper cutter. Eachsample was then peeled from the release paper and the excess polymerfilm was gently pulled from the edges of the sample. Each sample sheetwas then cut into ten 1 in (CD)×4 in (MD) strips.

[0189] Tensile Testing

[0190] The SinTech 1/D tensile tester with Testworks 3.03 versionsoftware was utilized for all sample testing. All testing was conductedin the machine direction using a 50 pound load cell and pneumatic,rubberized grips. The gage length was set at 3 in, and the crossheadspeed was 12 in/min. The wet samples were secured in the grips andstretched to failure. The peak load of each sample was recorded as thedata of interest. The data was not normalized to a 100% add-on level. Avalue of “0” was entered for the peak load if the sample was determinedto be dispersed. Samples were considered dispersed if individual stripscould not be removed from the salt solution intact due to lack ofstructural integrity.

[0191] The in-use strength of each sample was simulated by soaking thetensile samples in various salt solutions. The concentrations of thesalt solutions were chosen based upon a 2 wt % NaCl solution, which isequivalent to 0.34 M. The 0.68 M and 1.36 M NaCl solutions correspond to4 wt % and 8 wt %, respectively. The same molarities were chosen foreach of the other salts tested, though the weight percents are notnecessarily equivalent to the sodium chloride solutions. Salt solutionstested included 0.34 M NaCl, 0.68 M NaCl, 1.36 M NaCl, 0.34 M CaCl₂,0.68 M CaCl₂, 1.36 M CaCl₂, 0.34 M Na₂SO₄, 0.68 M Na₂SO₄, 1.36 M Na₂SO₄,0.17 M ZnCl₂, 0.34 M ZnCl₂, 0.51 M ZnCl₂, 0.34 M ZnSO₄, 0.17 MZnCl₂+0.17 M NaCl, 0.34 M LiCl, 0.34 M KCl, 0.34 M Na₃PO₄, and 0.34MMgCl₂.

[0192] Twenty-four tensile samples were placed into the salt solution tobe tested and allowed to soak overnight. Strips were added to the saltsolution one at a time in order to avoid sticking the samples together.Average soaking time was approximately 17 hours, and volume of soakingsolution was held constant at approximately 500 mL. Following theovernight soak, eight samples were tested directly to determine the peakload. This test simulated storage and in-use strength. Eight sampleswere placed into 200 ppm Ca²⁺/Mg²⁺ for 1 hour, and eight samples wereplaced into 200 ppm Ca ²⁺/Mg²⁺ for 3 hours. The peak load of the sampleswas measured following the soaking times. This test simulated disposalin the hardest water found in the United States.

[0193] Trigger Property

[0194] Polymer 1 showed salt sensitivity and significant strength inseveral solutions of sodium chloride. However, the polymer failed todisperse in 200 ppm Ca²⁺/Mg²⁺, as shown in Table 6 below. TABLE 6Tensile strength of acrylic acid based polymer (g/in) 1 hr. in 3 hr. inSalt Concentration Overnight soak hard water hard water 0.34 M 565 606648 0.68 M 639 649 634 1.36 M 722 600 608

[0195] It is suspected that the positive charge on the polymer promotesdissociation of carboxylic acid groups creating carboxylate anions.Complex formation between the carboxylate anion and Ca²⁺ leads tocross-linking, which prevents dispersion in hard water. In order toobtain hard water dispersibility, the acrylic acid was replaced withacrylamide, a water-soluble monomer. The acrylamide polymer (sample 2)showed trigger behavior in several salt solutions as summarized in Table7 below. TABLE 7 Tensile strength of acrylamide based polymer in varioussalt solutions (g/in) 1 hr. in 3 hr. in Salt Solution Overnight SoakHard Water Hard Water 0.34 M NaCl 311 0 0 0.68 M NaCl 317 0 0 1.36 MNaCl 429 0 0 0.34 M CaCl2 664 636 656 0.68 M CaCl2 635 662 666 1.36 MCaCl2 603 616 596 0.34 M Na2SO4 289 0 0 0.68 M Na2SO4 486 160 0 1.36 MNa2SO4 897 265 181 0.17 M ZnCl2 345 0 0 0.34 M ZnZl2 519 0 0 1.36 MZnCl2 661 0 0

[0196] General trends showed that increasing the concentration of thesalt solution increased the in-use strength of the polymer binder. Theperformance of the polymer is salt-specific. The polymer showed moderatestrength and good dispersibility in NaCl. The strength of the polymerincreased almost linearly with increasing Na₂SO₄ concentration, butreached good strength only at higher salt level. The dispersibility wentin the opposite direction. The polymer showed nice strength in ZnCl₂ andgood dispersibility. For CaCl₁₂, the polymer showed good strength,independent of salt concentration in the range of investigation, but nostrength loss was observed when placed in hard water. Both resultssuggested the cross-linking of the polymer caused by Ca²⁺. Acrylamidehas been generally regarded as salt insensitive, and its interactionwith Ca²⁺ is unknown. Based on the fact that the polymer dispersed wellin hard water when soaked in other salts, such as ZnCl₂ and NaCl, it isclear that retardation only occurs above certain Ca²⁺ concentrations.

[0197] One concern with acrylamide based polymer is the toxicity of theresidual acrylamide monomer in the polymer solution. To avoid the safetyconcern, acrylamide was removed from the composition. Sample 3-8 weremade with only three monomers: MQUAT, BA and EHA. Table 8 summarizedtheir trigger behavior. TABLE 8 Soluble properties of polymers of MQUAT,BA and EHA Sample 3 4 5 6 7 8 Solubility soluble soluble disperseddispersed triggered insol- uble

[0198] They differ greatly in the salt sensitivity as small changes incomposition can have large effects on the behavior of the polymer insolution. In general, their solubility decreases with decreasing MQUATcontent. Samples 3 and 4 were soluble in water even in very high saltconcentrations. Samples 5 and 6 were soluble in water and precipitatedat high salt level, but showed no strength. Sample 8 is insoluble inwater due to high hydrophobicity. Sample 7 had the best trigger propertyfor its delicate balance between the hydrophobic and hydrophilicmonomers. The behavior of the polymer in various salt solutions is shownin Table 9 below. TABLE 9 Performance of polymer 7 in various saltsolutions (g/in) Overnight Soak in 1 hr. Soak in 3 hr. Soak in SaltSolution Salt Solution Hard Water Hard Water  0.34 M LiCl 65 0 0  0.34 MNaCl 66 0 0  0.34 M KCl 81 0 0  0.34 M MgCl₂ 96 0 0  0.34 M CaCl₂ 183 00  0.34 M ZnCl₂ 861 33 25  0.17 M ZnCl₂ + 819 27 12  0.17 M NaCl 0.065 MZnCl₂ + 370 0 0  0.15 M NaCl  0.34 M Na₂SO₄ 0 0 0  0.34 M Na₃PO₄ 895 736699

[0199] The polymer displayed trigger property in monovalent salts,namely LiCl, NaCl and KCl, but it lacked any significant strength,falling far short of the minimum goal of 300 g/in for in-use strength.The performance in divalent cations was highly selective. The polymershowed unremarkable strength in MgCl₂ and CaCl₂, but displayed excellentstrength of over 800 g/in in ZnCl₂. The polymer also had excellenttriggerability in mixed salt of 0.1 7M ZnCl₂ and 0.17 M NaCl. When theZnCl₂ concentration was reduced to 0.065M, the strength was reduced. Thepolymer showed good hard water dispersibility from all those salts.

[0200] The effect of anions, especially multivalent anions, on thetrigger property was tested. The strength of the polymer in NaCl isunremarkable, though the dispersibility is good. The polymer possessedzero strength in Na₂SO₄. Following this discovery, the polymer was alsotested in ZnSO₄, in order to compare the exceptional strength of thepolymer in Zn²⁺ ion to its complete lack of strength in SO₄ ²⁻ ions. Thepolymer displayed zero strength in ZnSO₄ solution. The polymer forms anon-dispersible complex with phosphate ions, as it would not evendisperse after several hours in deionized water. Fortunately, phosphateion is extremely rare in waste water streams, and thus should pose noproblem for the dispersibility of the polymer once in a productapplication.

[0201] The “one pot” polymer, which contains 20% MQUAT, 40% BA and 40%EHA, displayed excellent strength of 896.6 g/in following the overnightsoak. However, the dispersibility of the “one pot” polymer was not asgood as that of the model polymer, as it still displayed 138.7 g/in ofstrength after one hour in hard water, and 90.2 g/in of strength after athree hour soak. Overall, the “one pot” polymer displays good triggerproperty. Although the result using the “one pot” were below the desiredresults, it is believed that a “one pot” polymer having acceptablestrength properties can be made by optimization of the polymer designand is therefore considered within the scope of the present invention.

EXAMPLE 2

[0202] Polymerization

[0203] Polymers were synthesized by free radical polymerization in thesame manner as described above. MQUAT, n-butyl acrylate (BA), and2-ethylhexyl acrylate (EHA) were utilized in ratios indicated in Table10.

[0204] Polymer composition was characterized by ¹³C NMR and thecompositions for each sample appear in Table 11. In most cases thepolymer compositions agree with the feed ratios within a few percentagepoints. This would be expected for a homogeneous solution polymerizationwhere all the monomers have a similar reactivity. TABLE 10 Polymer FeedRatios mole % Feed mole % Feed mole % Feed Sample NB # MQUAT BA EHA #1(028) 7421-028 20.0 40.0 40.0 #2 (041) 7421-041 15.8 42.1 42.1 #3 (046)7421-045 243   43.2 32.4 #4 (064) 7421-064 21.7 39.1 39.1 #5 (075)7421-075 12,6 58.9 28.5 #6 (083) 7421-083 20.0 80.0 0.0 #7 (094)7421-094 17.9 41.1 41.0 #8 (100) 7421-100 14.5 42.8 42.7 #9 (130)7421-130 27.3 30.4 36.3

[0205] TABLE 11 Polymer Composition mole % MQUAT mole % BA mole % EHASample Found Found Found #1 (028) 19.5 43.4 37.1 #2 (041) 18.1 46.4 35.5#3 (045) 25.7 43.3 31.0 #4 (064) 22.8 403 36.8 #5 (075) 12.1 59.4 28.5#6 (083) 20.2 79.8 0.0 #7 (094) 18.3 46.2 35.5 #8 (100) 13.3 47.6 39.1#9 (130) 25.6 40.5 33.9

[0206] Sample Preparation

[0207] Two base sheet materials were utilized to evaluate the cationicbinders. The first was a water-dispersible, wet-laid non-woven composedof BFF rayon fibers (1.5 d×25 mm). Each base sheet was cut to anapproximate size of 5.5 in (CD)×9 in (MD). A piece of release paper wasplaced onto a notepad, followed by a base sheet. Both pieces were tapedto the notepad with a single piece of Scotch tape. A #20 grooved,wire-wound rod was laid across the top of the sample. A strip of thepolymer solution to be tested was poured along the rod. With gentlepressure applied, the rod was then rolled down the length of the sample.Excess polymer was wiped off the bottom of the release paper, and thesample was placed into a forced air oven at 60° C. for at least 10minutes. The rod was cleaned between each sample as necessary.

[0208] Once the samples were dry, they were removed from the oven. Thetop part of each sample was removed with a paper cutter. Each sample wasthen peeled from the release paper and the excess polymer fill wasgently pulled from the edges of the sample. Each sample sheet was thencut into ten 1 in (CD)×4 in (MD) strips. Add-on for these samples was inthe range of 100%.

[0209] The second material used was an uncreped through-air dried(UCTAD) tissue basesheet made in the following fashion. A single ply,blended, uncreped through-air dried tissue basesheet was made generallyin accordance with U.S. Pat. No. 5,607,551 issued Mar. 4, 1997 toFarrington et al.(the disclosure of which is incorporated herein byreference). More specifically, 65 pounds (oven dry basis) of eucalyptushardwood Kraft fiber and 35 pounds (oven dried basis) of NorthernSoftwood Kraft (NSWK) fiber were dispersed in a pulper for 25 minutes ata consistency of 3% and refined before being transferred to a machinechest and diluted to a consistency of 1%. Prior to forming, the stockwas further diluted to approximately 0.1% consistency and transferred toa single layer headbox in such a manner as to provide a blended sheetcomprising 65% Eucalyptus and 35% NSWK. The formed web wasnon-compressively dewatered and rush transferred to a transfer fabrictraveling at a speed about 25 percent slower than the forming fabric.The web was then transferred to a through drying fabric and dried. Thetotal basis weight of the resulting sheet was 18.5 pounds per 2880 ft².

[0210] The binders were applied via spraying from a pressurized chamberand dried in a through-air drying oven at 165° C. for 2 min. Approximatebinder add-on was 20% for all UCTAD samples. Samples were then cut asnoted above.

[0211] Tensile Testing

[0212] The SinTech 1/D tensile tester with Testworks 3.03 versionsoftware was utilized for all sample testing. The testing was conductedusing the 60 pound load cell and pneumatic, rubberized grips. The gagelength was set at 2 in, and the crosshead speed was 12 in/min. The wetsamples were secured in the grips and stretched to failure. The peakload of each sample was recorded as the data of interest. A value of “0”was entered for the peak load if the sample was determined to bedispersed. Samples were considered dispersed if individual strips couldnot be removed from the salt solution intact due to lack of structuralintegrity.

[0213] The in-use strength of each sample was simulated by soaking thetensile samples in various salt solutions noted below. Disposal strengthor dispersibility was assessed by transferring samples soaked for aminimum of 12 hours in the salt solutions into deionized water or a hardwater simulant (200 ppm Ca²⁺/Mg²⁺). NaCl (4%) was utilized as well asseveral divalent metal salts were employed. ZnCl₂ at various levels wasemployed as well as MgCl₂, CaCl₂, ZnSO₄, and MgSO₄. Unless otherwisenoted, the testing methods were the same as disclosed in Example 1.

[0214] Trigger Properties

[0215] Data demonstrating the trigger properties for the co- andterpolymers in this study are shown in Tables 12 through 20. Tables 12and 13 show the cross-deckle wet tensile (Peak Load in g/inch), CDWT, inconcentrated NaCl and ZnCl₂ solutions. The order of the samples has beenrearranged to list them in order of increasing hydrophilicity. TABLE 12Wet Tensile Values (g/in.,) for NaCl Wetting Solutions (BFF Rayon) HardSample % MQUAT 5.2% NaCl 4% NaCl DI water water #5 (075) 12.1 826.5494.3 572.2 #8 (100) 13.3 1238.6 844.6 908.0 #2 (041) 18.1 241.1 158.7114.5 #7 (094) 18.3 736.9 28.0 173.1 #1 (028) 19.5 174.3 14.4 12.1 #6(083) 20.2 60.8 56.2 2.4 0.0 #4 (064) 22.8 28.2 41.1 0.9 1.9 #9 (130)25.6 9.1 0.0 0.0 #3 (045) 25.1 7.4 0.0 0.0

[0216] The trigger behavior in NaCl indicates a relatively narrow rangeof useful compositions At level of 18% MQUAT and below, the binders showgood web strength, but fail to re-disperse in DI water or hard water. Atmoderate incorporation of the MQUAT monomer (˜19-22%), some useful webstrength is indicated in 4% NaCl. The rayon webs subsequently loosevirtually all of their strength in DI and hard water. At relatively highincorporation of MQUAT (>25%), the web strength is below target valuesin 4% NaCl. The optimum trigger composition appears to containapproximately 20% MQUAT. Note that Sample #6 is a 20/80 MQUAT/BAcopolymer, while Sample #1 has a roughly equivalent amounts of BA andEHA. TABLE 13 Wet Tensile Values (g/in.) for 4% ZnCl₂ Wetting Solutions(BFF Rayon) Sample % MQUAT 4% ZnCl₂ DI water Hard water #5 (075) 12.11019.2 445.5 403.5 #8 (100) 13.3 1189.9 1180.2 658.1 #2 (041) 18.1.546.6 110.4 85.1 #7 (094) 18.3 1107.8 159.6 658.1 #1 (028) 19.5 743.326.5 29.2 #6 (083) 20.2 679.1 4.2 0.3 #4 (064) 22.8 981.2 5.0 4.9 #9(130) 25.6 726.7 9.2 8.9 #3 (045) 25.7 776.4 1.5 0.0

[0217] A much broader range of useful trigger compositions is evidentfor samples in a 4% ZnCl₂ solution. Samples containing ˜19 to 26% MQUATexhibit very good web strength in the salt solution, but completelyloose strength when transferred to DI water or hard water. Binders withapproximately 18% or less MQUAT still fail to disperse when transferredto deionized water (DI) water or hard water. One explanation for thediffering behavior in NaCl and ZnCl₂ is ionic strength. The ionicstrength (I) value for 4% ZnCl₂ is 0.88, as opposed to an I value of0.68 for 4% NaCl. The divalent Zn²⁺ ion has a larger effect on ionicstrength, and, thus, the two values are not equivalent at identicalweight percent.

[0218] It can be demonstrated, however, that ionic strength effectsalone cannot account for the difference in observed behavior. Table 12shows wet tensile values for Samples #4 and #6 in 5.2% NaCl (I=0.89),which has an almost identical I as 4% ZnCl₂. The binders still fail todevelop useful strength properties even in 5.2% NaCl. In fact, the wettensile values in 4% ZnCl₂ are still significantly higher.

[0219] To more systematically examine the effect of ZnCl₂ on theproperties of the binders, a study using 4, 3, 2, and 1% of the salt wasperformed. These data appear in Tables 14-17 below. At 4% and 3% ZnCl₂,Samples 1, 6, 4, 9, and 3 exhibit good trigger properties. Sample #7exhibits good web strength, but fails to dispersed completely in DI andhard water. Samples 2, 8, and 5 are too hydrophobic to exhibit triggerproperties. At 2% ZnCl₂, only Sample #1 exhibits good web strength anddispersibility. More hydrophilic samples fail to show sufficient webstrength, while more hydrophobic ones do not fully disperse. TABLE 14Repeat of Wet Tensile Values (g/in.) for 4% ZnCl₂ Wetting Solutions (BFFRayon). Sample 4% ZnCl₂ DI water Hard water #5 (075) 658.2 252.5  255.2 #8 (100) 709.9 337.5  352.2  #2 (041) n/a n/a n/a #7 (094) 675.1 50.9 70.4  #1 (028) 622.0 18.2  19.2  #6 (083) 561.6 3.3 2.4 #4 (064) 512.48.1 15.9  #9 (130) 574.1 0.0 0.0 #3 (046) 590.2 5.5 8.8

[0220] TABLE 15 Wet Tensile Values (g/in.) for 3% ZnCl₂ WettingSolutions (BFF Rayon). Sample 3% ZnCl₂ DI water Hard water #5 (075)729.1 268.4  281.5  #8 (1100) 671.3 281.7  318.7  #2 (041) n/a n/a n/a#7 (094) 676.9 43.3  63.5  #1 (028) 535.0 6.9 13.4  #6 (083) 324.5 0.00.0 #4 (064) 516.0 4.6 10.4  #9 (130) 288.5 0.0 0.0 #3 (046) 497.4 2.17.8

[0221] In 1% ZnCl₂, Sample #1 indicates some trigger property, but thelevel of strength developed is below preferred levels. Interestingly, atthis low level of salt, Sample #7 exhibits some useful triggerproperties. The strength is in the low range and the dispersibilty isslightly less than desired, but the effect is clear. TABLE 16 WetTensile Values (g/in.) for 2% ZnCl₂ Wetting Solutions (BFF Rayon),Sample 2% ZnCl₂ DI water Hard water #5 (075) 615.9 177.9  253.3  #8(100) 651.6 322.9  347.6  #2 (041) n/a n/a n/a #7 (094) 552.0 34.5 71.5  #1 (028) 385.8 6.0 8.9 #6 (083)  0.0 0.0 0.0 #4 (064)  89.9 0.04.5 #9 (130)  0.0 0.0 0.0 #3 (045)  12.4 0.0 0.0

[0222] TABLE 17 Wet Tensile Values (g/in.) for 1% ZnCl₂ WettingSolutions (BFF Rayon). Sample 1% ZnCl₂ DI water Hard water #5 (075)474.09  293.02  279.90  #8 (100) 482.82  258.83  298.85  #2 (041) n/an/a n/a #7 (094) 200.91  9.36 24.90  #1 (028) 48.42  0.00 0.00 #6 (083)0.00 0.00 0.00 #4 (064) 0.00 0.00 0.00 #9 (130) 0.00 0.00 0.00 #3 (045)0.00 0.00 0.00

[0223] It is apparent that the hydrophobic/hydrophilic balance is veryimportant with these cationic binders, even though the trigger range andlevel of salt necessary are much broader. To further demonstrate thiseffect, MQUAT polymers with 0, 50, and 20 mole % BA were synthesized andtested. These data appear in Table 9. The MQUAT homopolymer and the50/50 BA copolymer fail to show sufficient strength in the web. The20/80 MQUAT/BA copolymer exhibits good strength and dispersibility in 4%ZnCl₂. Clearly, the level of hydrophobe plays a role in the adhesiveproperties of these binders. TABLE 18 Effect of BA Co-monomer on WetTensile (BFF Rayon). CDWT CDWT mole % mole % (g/in.) (g/in.) Feed FeedCDWT DI Hard Sample NB# MQUAT BA (g/in.)ZnCl₂ Water Water #10 6787-34 2080 560.3 0 0 #12 6787-54 50 50 0 0 0 #11 6787-38 100 0 0 0 0

[0224] An UCTAD tissue substrate was also examined using −20% add-on ofthe 20/80 MQUAT/BA copolymer (#6). CDWT as a function of percent ZnCl₂solution is shown in Table 19. In general, the same trends seen with therayon basesheets are apparent. However, the dispersibility for 4% and 3%ZnCl₂ seems to suffer on the UCTAD basesheet. At 2% ZnCl₂, the systemactually seems to show a good balance of strength and re-dispersibility.The strength falls below an acceptable level when 1% ZnCl₂ is employed.TABLE 19 Effect of % ZnCl₂ on CDWT for UCTAD tissue using Sample #6 %ZnCl₂ Salt solution DI water Hard water 4 396.7 n/a 36.4 3 522.3 18.4 34 2 296.2 2.2 11.7 1 55.9 0.1 0.2

[0225] The effect of other divalent ions, as well as the effect ofdifferent counterions is shown in Table 20. Good strength is apparent in4% ZnCl₂, as noted before. Also, other salts of divalent ions, such asMgCl₂ and CaCl₂ can provide trigger properties at acceptable strengthlevels. However, when the sulfate salts of these ions are employed,insufficient strength or trigger properties result. Apparently, thetrigger behavior in these systems is mediated by both the cation and theanion of the salt employed. TABLE 20 Effect of divalent ions andcounterions on CDWT using Sample #6 on UCTAD tissue Salt Type 4%Solution DI water Hard water ZnCl₂ 364.2 37.6 49.4 MgCl₂ 133.9 6.6 8.6CaCl₂ 93.3 3.9 7.4 ZnSO₄ 9.8 7.9 13.3 MgSO₄ 15.6 8.8 15.4

[0226] These results seem to indicate “ion specific” interactions ratherthan the “salting-out” effect seen in previous systems. Although ionicstrength may play a role here, the data presented here clearly indicatesa new type of trigger mechanism based on hydrophobic associations andion-specific interactions.

EXAMPLE 3

[0227] Polymerization

[0228] Cationic triggerable polymers were synthesized by free radicalpolymerization in the same manner as described above. MQUAT, n-butylacrylate (BA), and 2-ethylhexyl acrylate (EHA) were utilized in thefollowing ratios: MQUAT 20 mole percent, BA 40 mole percent and EHA 40mole percent. It is stable in high salt solutions, such as 4 weightpercent ZnCl₂, and is soluble in water when the salt concentration dropsbelow a certain level, such as 0.5 weight percent. Because of the natureof the charge groups the polymer carries, its dispersibility isvirtually unaffected by the presence of divalent cations, such as Ca²⁺and Mg²⁺ up to 200 ppm, and, therefore, the polymer performs well evenin the hardest water found in the United States households.

[0229] Wet Wipe Sample Preparation

[0230] To make a wet wipe product, the ion-sensitive cationic polymerwas applied in an aqueous solution to a substrate by spraying. Thesubstrate was a water-dispersible, wet-laid non-woven composed of BFFrayon fibers (1.5×25 mm). Two different binder solution were prepared.The first solution was an aqueous solution of the ion-sensitive polymer.The other solution was an aqueous solution of the ion-sensitive polymer(75 weight percent) and a co-binder (25 weight percent) in the form ofan emulsion polymer. The co-binder provides several advantages to thepolymer system, including rheology modification for better sprayapplication, better binder penetration for higher strength, tackreduction and cost savings.

[0231] Selection of the emulsion system for the co-binder is critical.The emulsion system of the co-binder must not interact with theion-sensitive cationic polymer such that it interferes with the triggerproperty. Three emulsion-based polymers were tested. Rovene 4817 astyrene butadiene copolymer manufactured by Mallard Creek Polymers,Charlotte, N.C., and Rhoplex P-376 a styrene acrylate copolymermanufactured by Rohm and Haas, Philadelphia, Pa. The combination of thecationic polymer and the Rovene 4817 and the Rhoplex P-376 caused severprecipitation of the binder from the aqueous solution. It was suspectedthat the anionic emulsion surfactants used in the Rovene 4817 and theRhoplex P-376 may have interacted with the cationically charged polymerthrough electrostatic forces, thus resulting in the precipitation of thebinder out of suspension. It was therefore determined that theseemulsion polymers were not suitable for use with the cationicion-sensitive polymer of the present invention.

[0232] The third emulsion polymer that was investigated was Duroset RB®manufactured by National Starch and Chemical Company. Duroset RB® is anethylene vinyl acetate copolymer. When the Duroset RB® was combined withthe cationic polymer, only a small amount of precipitation was observed,and did not interfere with the trigger property of the binder system.

[0233] Two different samples were prepared. One sample of the substrateincluded a binder made from only the cationic polymer; the othersubstrate contained a binder made from 75 weight percent cationicpolymer and 25 weight percent Duroset RB®. The samples were prepared inthe same manner as disclosed in co-pending U.S. patent applicationSerial No. 09/564,939 assigned to Kimberly-Clark (the disclosure ofwhich is incorporated herein by reference).

[0234] The samples were soaked in an aqueous solution containing 4weight percent ZnCl₂. The samples were then soaked in water containing200 ppm Ca²⁺/Mg²⁺. The samples were then tested for tensile strength.The results of this test are shown in Table 21 below. TABLE 1 TriggerPerformance of Cationic Binder 1 hr soak in 3 hr soak in Sample 4% ZnCl₂hard water hard water 100% Binder 861 33 25 75% Binder/25% Duroset RB ®714 11 0

[0235] The foregoing test results show that the tensile strength wasreduced by about 20% with the addition of 25% Duroset RB®. Both samplesshowed acceptable wet strength in the 4% ZnCl₂ solution. After one hourof soaking in 200 ppm Ca²⁺/Mg²⁺ solution, the peak load decreasedsignificantly. The strength was practically zero. After three hours ofsoaking, the sample containing the Duroset RB® was fully dispersedwithout shaking.

[0236] It is contemplated that emulsion polymers that use only a smallamount of anionic surfactant or use a weak anionic surfactant may beused as the co-binder in the present invention as long as they do notcause precipitation to such an extent that it interferes with thetrigger property of the polymer composition. It is also specificallycontemplated that other emulsion polymers using nonionic or cationicsurfactant systems may also be used as the co-binder in the presentinvention.

[0237] It should be understood, of course, that the foregoing relatesonly to certain disclosed embodiments of the present invention and thatnumerous modifications or alterations may be made therein withoutdeparting from the spirit and scope of the invention as set forth in theappended claims.

What is claimed is:
 1. A composition comprising a triggerable cationicpolymer, wherein the composition is triggerable.
 2. A compositioncomprising a triggerable cationic polymer, wherein the polymerformulation is insoluble in a solution containing a sufficient amount ofan insolublizing agent and is dispersible in water containing up toabout 500 ppm of one or more multivalent ions.
 3. A compositioncomprising a triggerable cationic polymer, wherein the polymerformulation is insoluble in an aqueous solution containing at leastabout 0.5 weight percent of an insolublizing agent and is dispersible inwater containing up to about 500 ppm of one or more multivalent ions. 4.A composition comprising a triggerable cationic polymer, wherein thepolymer formulation is insoluble in a neutral salt solution containingat least about 2 weight percent salt; and wherein the polymerformulation is soluble in water containing up to about 500 ppm of one ormore multivalent ions.
 5. A composition comprising a triggerablecationic polymer, wherein the polymer formulation has wet strength in aneutral salt solution containing at least about 2 weight percent salt;and wherein the polymer formulation is dispersible in hard or softwater.
 6. A composition comprising a triggerable cationic polymer,wherein the polymer formulation is insoluble in water that contains asufficient amount of an insoubilizing agent; and wherein the polymerformulation is soluble in water containing an insufficient amount of aninsolubilizing agent.
 7. A binder composition for binding fibrousmaterial into an integral web, said binder composition comprising thecomposition of claim
 1. 8. A nonwoven fabric comprising fibrous materialand a binder material, said binder material comprising the compositionof claim
 1. 9. A fibrous substrate comprising: fibrous material; and abinder composition for binding said fibrous material into an integralweb, said binder composition comprising a triggerable cationic polymer.10. A water-dispersible article comprising the fibrous substrate ofclaim
 9. 11. A wet wipe comprising: a fibrous material; a bindercomposition for binding said fibrous material into an integral web, saidbinder composition comprising a triggerable cationic polymer; and saidfibrous material being wetted by a wetting solution containing at leastabout 2 weight percent salt.
 12. A method of making a wet wipecomprising: forming a substrate of fibrous material; applying to saidsubstrate a binder composition for said fibrous material comprising atriggerable cationic polymer; and applying to said substrate a wettingsolution containing a sufficient amount of an insolublizing agent suchthat said polymer is insoluble in said wetting solution.
 13. A method ofmaking a wet wipe comprising: forming a substrate of fibrous material;applying to said substrate a binder composition for said fibrousmaterial comprising a triggerable cationic polymer; and applying to saidsubstrate a wetting solution containing at least about 2 weight percentsalt.
 14. A method comprising applying to a substrate of fibrousmaterial a binder composition for said fibrous material comprising atriggerable cationic polymer.
 15. A composition comprising a triggerablecationic polymer, wherein the polymer formulation has wet strength in anaqueous solution containing at least about 0.5 weight percent of aninsolublizing agent; and wherein the polymer formulation is dispersiblein hard or soft water.
 16. A composition comprising a triggerablecationic polymer, wherein the polymer formulation has wet strength in anaqueous solution independent of the pH of said aqueous solution, saidaqueous solution containing at least about 0.5 weight percent of aninsolubilizing agent and wherein the polymer formulation is dispersiblein hard or soft water.
 17. A binder composition for binding fibrousmaterial into an integral web, said binder composition comprising thecomposition of claim
 15. 18. A nonwoven fabric comprising fibrousmaterial and a binder material, said binder material comprising thecomposition of claim
 15. 19. A wet wipe comprising: a fibrous material;a binder composition for binding said fibrous material into an integralweb, said binder composition comprising a triggerable cationic polymer;and said fibrous material being wetted by a wetting solution containingat least about 0.5 weight percent of an insolublizing agent.
 20. Amethod of making a wet wipe comprising: forming a substrate of fibrousmaterial; applying to said substrate a binder composition for saidfibrous material comprising a triggerable cationic polymer; and applyingto said substrate a wetting solution containing at least about 0.5weight percent of an insolublizing agent.
 21. A composition comprising atriggerable cationic polymer, wherein the polymer formulation isinsoluble in an aqueous solution containing at least about 0.5 weightpercent of a divalent metal salt capable of forming a complex anion.